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SYNTHETIC INORGANIC
CHEMISTRY
Developments in Inorganic Chemistry
SYNTHETIC
INORGANIC
CHEMISTRY
New Perspectives
Edited by
EWAN J. M. HAMILTON
The Ohio State University at Lima, Lima, OH, United States
SERIES EDITOR
NARAYAN S. HOSMANE
Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Copyright © 2021 Elsevier Inc. All rights reserved.
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This book and the individual contributions contained in it are protected under copyright by the
Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical
treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described herein.
In using such information or methods they should be mindful of their own safety and the safety
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To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors,
assume any liability for any injury and/or damage to persons or property as a matter of products
liability, negligence or otherwise, or from any use or operation of any methods, products,
instructions, or ideas contained in the material herein.
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library
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A catalog record for this book is available from the Library of Congress
ISBN: 978-0-12-818429-5
For Information on all Elsevier publications

visit our website at https://www.elsevier.com/books-and-journals
Publisher: Susan Dennis

Acquisitions Editor: Emily M. McCloskey
Editorial Project Manager: Lindsay Lawrence
Production Project Manager: Bharatwaj Varatharajan
Cover Designer: Mark Rogers
Typeset by MPS Limited, Chennai, India
Contents
List of contributors ix
Foreword xiii
Preface xv
Section 1
Non-precious metals in catalysis
1. Homogeneous aluminum and iron catalysts for the synthesis of
organic molecules and biodegradable polymers
Xiao Wu, Katie J. Lamb, Agustı́n Lara-Sánchez, Carlos Alonso-Moreno,
Michael North and José A. Castro-Osma
1.1 Introduction 3
1.2 Aluminum-based catalysts 4
1.3 Iron-based catalysts 20
1.4 Conclusions 33
References 33
Section 2
Smart inorganic polymers
2. Polyphosphazenes: macromolecular structures, properties,
and their methods of synthesis
Aitziber Iturmendi, Helena Henke, George S. Pappas and Ian Teasdale
2.1 Introduction 47
2.2 Synthesis of poly(organo)phosphazenes 48
2.3 Advanced architectures 54
2.4 Cyclomatrix organophosphazenes 63
2.5 (Bio)degradable poly(organo)phosphazenes 72
2.6 Water-soluble poly(organo)phosphazenes 78
2.7 Soft materials 83
2.8 Conclusions and outlook 89
References 90
v
vi Contents
Section 3
Inorganic chemistry in ionic liquids
3. Application of ionic liquids in inorganic synthesis
Di Li and Wenjun Zheng
3.1 Introduction 105

3.2 Advantages and key factors of the structural regulation
mechanism of ionic liquids in inorganic synthesis 108
3.3 Ionic liquids assisted synthesis of nanomaterials 110
3.4 Summary 123
References 123
Section 4
Metal-organic frameworks
4. Wettability control of metal-organic frameworks
Qi Sun and Shengqian Ma

4.2 Wettability of metal-organic framework surfaces 133
4.3 Synthesis of hydrophobic metal-organic framework materials 134
4.4 Linker-based hydrophobic metal-organic frameworks 136
4.5 Induction of hydrophobicity by postsynthetic modification 140
4.6 Introduction of external surface corrugation by use of a
hydrophobic unit 144
4.7 Hydrophobic metal-organic framework composites 147
4.8 Potential applications of hydrophobic metal-organic frameworks
and their composites 154
4.9 Gas separation/storage 154
4.10 Oil spill cleanup 157
4.11 Catalysis 158
4.12 Conclusions and perspectives 160
References 161
Section 5
Frustrated Lewis pairs and small molecule activation
5. Rivaling transition metal reactivity—an exploration
of frustrated Lewis pairs chemistry
Meera Mehta and Christopher B. Caputo

Contents vii
5.2 Evidence that unique chemistry was possible with main-group

Lewis acids and bases 170
5.3 The discovery of reversible dihydrogen activation and catalysis 172
5.4 Small molecule activation 174
5.5 Mechanistic insights into frustrated Lewis pair small molecule activation 185
5.6 Frustrated Lewis pair mediated CsH bond activation 187
5.7 Immobilization of frustrated Lewis pairs 189
5.8 Unconventional Lewis acid partners 192
5.9 Transition metal frustrated Lewis pair systems 202
5.10 What are the requirements for frustration? 206
5.11 Outlook 209
References 210
Section 6
New inorganic therapeutics, I
6. Ruthenium and iron metallodrugs: new inorganic and
organometallic complexes as prospective anticancer agents
Andreia Valente, Tânia S. Morais, Ricardo G. Teixeira, Cristina P. Matos,
Ana Isabel Tomaz and M. Helena Garcia

6.2 Novel octahedral Ru(III)/Fe(III)-based prospective drug candidates 233
6.3 Designing metallodrugs with the {M(II)(Cp)} scaffold 242
6.4 General synthetic procedures for ruthenium and iron prospective
metallodrugs 259
6.5 Conclusions and final comments 265
Acknowledgments 266
References 266
Section 7
New inorganic therapeutics, II
7. Functional nanocomposites: promising candidates for cancer
diagnosis and treatment
Okan Icten

7.2 Synthesis techniques for preparation of nanocomposites 282
7.3 Surface modification 299
7.4 Cancer diagnosis and treatment applications of
functional nanocomposites 308
References 327
viii Contents
Section 8
Advances in fundamental main group chemistry, I
8. Recent advances in the selective functionalization of anionic
icosahedral boranes and carboranes
Mustapha Hamdaoui, Rajesh Varkhedkar, Jizeng Sun, Fan Liu
and Simon Duttwyler

8.2 BsH activation for the functionalization of anionic boron clusters 349
8.3 Directing group-controlled formation of organometallic complexes of the
monocarborane anion 354
8.4 Transition metal-catalyzed functionalization of anionic boron clusters 364
8.5 Outlook 384
Acknowledgements 385
References 385
Section 9
Advances in fundamental main group chemistry, II
9. Coordination of N-heterocyclic carbene to Si Si
and P P multiple bonded compounds
Anukul Jana

9.2 NHC coordination to a Si Si triple bonded compound 396
9.3 Reversible NHC coordination to Si Si double bonded compounds 398
9.4 Reversible NHC coordination to PsP double bonded compounds 400
9.5 Conclusions 425
References 425
Section 10
Bioinspired inorganic synthesis
10. Bioinorganic and bioinspired solid-state chemistry:
from classical crystallization to nonclassical synthesis concepts
Stephan E. Wolf
10.1 Introduction: creatures proficient in inorganic solid-state chemistry 433

10.2 Biominerals: basic principles of bioinorganic solid-state chemistry 437
10.3 From biomineralizing organism to bioinspired in vitro syntheses 447
10.4 From solutes to solids: conclusions and outlook 471
References 472
Index 491
List of contributors
Carlos Alonso-Moreno Departamento de Quı́mica Inorgánica, Orgánica y

Bioquı́mica, and Centro de Innovación en Quı́mica Avanzada (ORFEO–CINQA),
Facultad de Farmacia, Universidad de Castilla-La Mancha, Albacete, Spain
Christopher B. Caputo Department of Chemistry, York University, Toronto,

ON, Canada
José A. Castro-Osma Departamento de Quı́mica Inorgánica, Orgánica y

Bioquı́mica, and Centro de Innovación en Quı́mica Avanzada (ORFEO–CINQA),
Facultad de Farmacia, Universidad de Castilla-La Mancha, Albacete, Spain
Simon Duttwyler Department of Chemistry, Zhejiang University, Hangzhou,

P.R. China
M. Helena Garcia Centro de Quı́mica Estrutural and Departamento de

Quı́mica e Bioquı́mica, Faculdade de Ciências, Universidade de Lisboa, Campo
Grande, Portugal
Mustapha Hamdaoui Department of Chemistry, Zhejiang University,

Hangzhou, P.R. China
Helena Henke Institute of Polymer Chemistry, Johannes Kepler University,

Linz, Austria
Okan Icten Hacettepe University, Ankara, Turkey
Aitziber Iturmendi Institute of Polymer Chemistry, Johannes Kepler

University, Linz, Austria
Anukul Jana Tata Institute of Fundamental Research Hyderabad, Hyderabad,

India
Katie J. Lamb Green Chemistry Centre of Excellence, Department of

Chemistry, The University of York, York, United Kingdom
Agustı́n Lara-Sánchez Departamento de Quı́mica Inorgánica, Orgánica y

Bioquı́mica, and Centro de Innovación en Quı́mica Avanzada (ORFEO-CINQA),
Facultad de Ciencias y Tecnologı́as Quı́micas, Universidad de Castilla-La
Mancha, Ciudad Real, Spain
Di Li Institute for Energy Research, Jiangsu University, Zhenjiang, P.R. China
Fan Liu Department of Chemistry, Zhejiang University, Hangzhou, P.R. China
ix
x List of contributors
Shengqian Ma Department of Chemistry, University of South Florida, Tampa,

FL, United States
Cristina P. Matos Centro de Ciências e Tecnologias Nucleares (C2TN),

Instituto Superior Técnico, Universidade de Lisboa, Bobadela
LRS, Portugal
Meera Mehta Department of Chemistry, The University of Manchester,

Manchester, United Kingdom
Tânia S. Morais Centro de Quı́mica Estrutural and Departamento de Quı́mica e

Bioquı́mica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande,
Portugal
Michael North Green Chemistry Centre of Excellence, Department of

Chemistry, The University of York, York, United Kingdom
George S. Pappas Institute of Polymer Chemistry, Johannes Kepler University,

Linz, Austria
Jizeng Sun Department of Chemistry, Zhejiang University, Hangzhou,

P.R. China
Qi Sun Department of Chemistry, University of South Florida, Tampa, FL,

United States; College of Chemical and Biological Engineering, Zhejiang
University, Hangzhou, P.R. China
Ian Teasdale Institute of Polymer Chemistry, Johannes Kepler University,

Linz, Austria
Ricardo G. Teixeira Centro de Quı́mica Estrutural and Departamento de

Grande, Portugal
Ana Isabel Tomaz Centro de Quı́mica Estrutural and Departamento de

Grande, Portugal
Andreia Valente Centro de Quı́mica Estrutural and Departamento de Quı́mica

e Bioquı́mica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande,
Portugal
Rajesh Varkhedkar Department of Chemistry, Zhejiang University,

Hangzhou, P.R. China
Stephan E. Wolf Department of Materials Science and Engineering, Institute

for Glass and Ceramics, Friedrich-Alexander-University Erlangen-Nürnberg
(FAU), Erlangen, Germany
Xiao Wu Green Chemistry Centre of Excellence, Department of Chemistry,

The University of York, York, United Kingdom
List of contributors xi
Wenjun Zheng Department of Chemistry, Key Laboratory of Advanced
Energy Materials Chemistry (MOE), TKL of Metal and Molecule-Based Material
Chemistry, College of Chemistry, Nankai University, Tianjin, P.R. China;
Collaborative Innovation Center of Chemical Science and Engineering, Nankai
University, Tianjin, P.R. China
Foreword
I was delighted to be asked to write this Foreword to Synthetic

Inorganic Chemistry: New Perspectives, the first volume in the Elsevier
series Developments in Inorganic Chemistry. The volume editor, Prof. Ewan
J. M. Hamilton, the series editor, Prof. Narayan S. Hosmane, and I share
several things—a fulfilling early-career association with the Department
of Chemistry at the University of Edinburgh, Scotland; an enduring love
of polyhedral boron chemistry; and the firm belief that a full appreciation
of what inorganic chemistry is and can do naturally begins with the
synthesis of new molecules and materials. In the last respect, it is entirely
fitting that the first volume in this new series should be devoted to the
art of inorganic synthesis. The tremendous diversity of synthetic inor-
ganic chemistry is clearly evident from the range of subjects covered in
the following 500 pages, organised into 8 themes and 10 chapters written
by internationally leading experts. It will be both an invaluable reference
work to those working in the specific areas covered and a clear beacon to
others of the importance of synthetic inorganic chemistry as a key
enabling interdisciplinary subject.
Alan J. Welch
Heriot-Watt University, Edinburgh, United Kingdom
March 2021
xiii
Preface
While august multivolume collections such as the Comprehensive

Inorganic Chemistry series or Modern Synthetic Inorganic Chemistry repre-
sent tremendous resources that succeed in providing in-depth and
somewhat exhaustive coverage of all aspects of inorganic chemistry, the
aim of this book is somewhat different.
If one were to ask a layperson to visualize and describe a chemist at
work in their laboratory, one would likely hear a description of some-
one in a lab coat and goggles, with a suitably wild hairstyle, ministering
over a collection of test tubes and other strange pieces of glassware
filled with a variety of different colored (and most often bubbling!)
liquids. The telling thing, however, is that the ubiquity of color in these
compounds suggests that the “research” going on here revolves around
inorganic compounds.
Yet if we were to then ask the same layperson what this (inorganic)
chemist may be seeking to make or to learn, or what advances or bene-
fits to society accrue from chemical research, we are most likely to hear
about the development of what are essentially organic pharmaceutical
compounds. What, then, is our synthetic inorganic chemist up to?
In this volume, we seek to give a broad sense of the themes, scale,
scope, and excitement of today’s synthetic inorganic chemistry. The
audience for the book are chemists and students of chemistry for whom
inorganic chemistry may not (yet?) be their core subdiscipline. As will
be clear from the following short introduction to some of the topics that
lie within these pages, there exists a significant degree of crossover
between synthetic inorganic chemistry and other disciplines such as
catalysis, medicinal chemistry, and materials science, and, of course,
between subdivisions of inorganic chemistry itself. Indeed, the obser-
vant reader will even find the authors of one chapter refer to the work
of other authors, known for their work in what would appear at first
glance to be a very different area of endeavor. (I will leave it to the
reader to find this in the text!).
While the preparation of new transition metal-based catalysts has been
at the forefront of inorganic chemistry for decades, the need to develop
catalytic systems around earth-abundant, nonprecious metals has never
been greater. Chapter 1, Homogeneous Aluminum and Iron Catalysts for
the Synthesis of Organic Molecules and Biodegradable Polymers, describes
some recent progress in the preparation of homogeneous catalysts based
xv
xvi Preface
on aluminum and iron for a variety of bond-forming and polymerization

reactions.
On the subject of polymers, Chapter 2, Polyphosphazenes:
Macromolecular Structures, Properties, and Their Methods of Synthesis,
provides an introduction to the synthesis of the class of inorganic poly-
mers known as polyphosphazenes, based on an alternating P N back-
bone. Recent synthetic advances described herein have permitted rational
design of a wide range of macromolecular structures with varied physico-
chemical properties, paving the way for continued growth in this area.
Another area in which the development of new synthetic methods
has enabled expansion into the production of materials with different
structural motifs has been by the use of ionic liquids. Chapter 3,
Application of Ionic Liquids in Inorganic Synthesis, provides an over-
view of the function of ionic liquids as solvents, templates, and also
potential precursors in the synthesis of a variety of inorganic materials
featuring 0D to 3D architectures that find application in, for example, a
variety of photocatalytic processes.
Metal-organic frameworks (MOFs) are a class of materials to which
the talents of synthetic inorganic chemists have been brought to bear in
recent years. A huge variety of these fascinating compounds have
already been prepared, with a great range of potential applications in
separations, sensing, catalysis, etc. A significant drawback to wider
practical adoption of these materials, however, is their limited stability
in aqueous (or merely ambient) environments. Control over the wetta-
bility of MOFs is, therefore, a crucial issue, and synthetic approaches
toward this necessary goal are addressed in Chapter 4, Wettability
Control of Metal-Organic Frameworks.
The theme of catalysis is never far from the mind of the modern syn-
thetic inorganic chemist, and this recurs in the work described in
Chapter 5, Rivaling Transition Metal Reactivity—An Exploration of
Frustrated Lewis Pairs Chemistry. While Chapter 1, Homogeneous
Aluminum and Iron Catalysts for the Synthesis of Organic Molecules
and Biodegradable Polymers, describes catalytic systems that avoid pre-
cious metals, the concept of frustrated Lewis pairs represents a
completely different approach that arguably goes one better by using
cleverly designed combinations of main group elements to effect small
molecule activation. The frustrated Lewis pair concept is also extended
to include Lewis acidic early transition metals as well as examples of
later transition metals functioning in a Lewis basic role, so broadening
our concept of what constitutes a frustrated Lewis pair.
Chapter 6, Ruthenium and Iron Metallodrugs: New Inorganic and
Organometallic Complexes as Prospective Anticancer Agents, and
Chapter 7, Functional Nanocomposites: Promising Candidates for
Cancer Diagnosis and Treatment, share the conceptual spirit of applying
inorganic synthesis to the arena of anticancer therapeutics. These two
Preface xvii
chapters, however, take radically different approaches to this crucially

important problem. In Chapter 6, Ruthenium and Iron Metallodrugs:
New Inorganic and Organometallic Complexes as Prospective
Anticancer Agents, we are introduced to two broad classes of new
molecular compounds based on iron and ruthenium as potential metal-
lodrugs, which might circumvent the significant drawbacks associated
with prevailing platinum-based chemotherapy. Chapter 7, Functional
Nanocomposites: Promising Candidates for Cancer Diagnosis and
Treatment, describes the methods of synthesis of nanocomposite materi-
als and their use in an array of diagnostic and multimodal therapeutic
techniques, including MRI, fluorescence imaging, hyperthermia, boron
and gadolinium neutron capture therapy, and photodynamic therapy.
The mention of boron neutron capture therapy brings us neatly to
Chapter 8, Recent Advances in the Selective Functionalization of Anionic
Icosahedral Boranes and Carboranes, the first of our chapters on funda-
mental main group synthesis. Here, new methodologies are presented
that describe the selective functionalization of icosahedral (monocarbon)
carborane and borane clusters. Despite these cluster cores having been
known for decades, the work described in Chapter 8, Recent Advances in
the Selective Functionalization of Anionic Icosahedral Boranes and
Carboranes, represents an important stride in their controlled derivatiza-
tion and opens the door to their continued development.
Our second chapter on fundamental main group synthesis describes
work aimed at understanding the nature of multiple bonds between
nonmetals. Specifically, Chapter 9, Coordination of N-Heterocyclic
Carbene to Si Si and P P Multiple Bonded Compounds, describes the
manner in which multiply bonded Si Si and P P moieties interact with
N-heterocyclic carbenes and the careful study required to reveal the
complex nature of these (often equilibrium-based) systems.
The book concludes with Chapter 10, Bioinorganic and bioinspired
solid-state chemistry: from classical crystallization to nonclassical syn-
thesis concepts, developing the concepts of bioinspired solid-state
chemistry. This new branch of bioinorganic chemistry investigates
biomineralization and the application of nonclassical biomimetic techni-
ques that are capable of producing solid-state inorganic materials under
much milder conditions than those typically employed in traditional
solid-state synthetic protocols.
It has been my great pleasure to work with all of the authors who
have contributed these fine chapters. I have learned a great deal about
many aspects of synthetic inorganic chemistry from them, and I am
humbled by their expertise and dedication to their respective fields of
study. I believe we are very fortunate to have succeeded in enlisting
experts of their caliber to write these enlightening chapters for us.
Ewan J. M. Hamilton
The Ohio State University at Lima, Lima, OH, United States
March 2021
S E C T I O N 1
Non-precious metals in
catalysis
C H A P T E R
1
Homogeneous aluminum and
iron catalysts for the synthesis of
organic molecules and
biodegradable polymers
Xiao Wu1, Katie J. Lamb1, Agustı́n Lara-Sánchez2,
Carlos Alonso-Moreno3, Michael North1 and José
A. Castro-Osma3
1
Green Chemistry Centre of Excellence, Department of Chemistry, The
University of York, York, United Kingdom, 2Departamento de Quı́mica
Inorgánica, Orgánica y Bioquı́mica, and Centro de Innovación en Quı́mica
Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologı́as Quı́micas,
Universidad de Castilla-La Mancha, Ciudad Real, Spain, 3Departamento de
Quı́mica Inorgánica, Orgánica y Bioquı́mica, and Centro de Innovación en
Quı́mica Avanzada (ORFEO CINQA), Facultad de Farmacia, Universidad
de Castilla-La Mancha, Albacete, Spain
1.1 Introduction
The use of metal complexes as catalysts in organic synthesis and polymer

chemistry has attracted much attention over the last few decades and there
have been remarkable achievements in this area.1 20 However, most catalytic
processes rely on the use of precious metals such as iridium, ruthenium,
platinum, and palladium among others.21 27 Moreover, the price of transi-
tion and rare-earth elements has increased over the last decade. Therefore
the development of inexpensive and Earth-abundant metal-containing
Synthetic Inorganic Chemistry

DOI: https://doi.org/10.1016/B978-0-12-818429-5.00002-8 3 © 2021 Elsevier Inc. All rights reserved.
4 1. Homogeneous aluminum and iron catalysts for the synthesis of organic molecules
complexes as industrial catalysts for the production of organic molecules or

biodegradable polymeric materials has increased in recent years.28 31
Aluminum and iron are among the most abundant metals in the Earth’s
crust and are significantly cheaper than noble metals that are currently used
in chemical processes.28 In these metal complexes, the metal center is gener-
ally stabilized by the coordination of a broad variety of ligands that allow
their use as catalysts for both achiral and asymmetric transformations.32 34
In this chapter, we will focus on the use of aluminum and iron complexes as
catalysts for CsC and C heteroatom bond forming and ring-opening poly-
merization (ROP) and copolymerization (ROCOP) reactions.
1.2 Aluminum-based catalysts
Aluminum compounds have been used as catalysts for a broad range of

chemical transformations and some excellent reviews regarding
aluminum-catalyzed reactions have been reported in the literature.35 38 In
this section we will cover some of the most important reactions catalyzed
by aluminum such as reactions of three-membered ring heterocycles with
heterocumulenes, hydroelementation reactions, and ROP processes.
1.2.1 Reaction of three-membered ring heterocycles with

heterocumulenes
Salen and related ligand-based aluminum complexes are well-
studied catalysts for the reaction between epoxides and carbon dioxide.
The general mechanism for the synthesis of cyclic carbonates from epox-
ides and carbon dioxide is presented in Scheme 1.1. Thus the catalysts
SCHEME 1.1 General mechanism for cyclic carbonate synthesis.
1. Non-precious metals in catalysis

could either be a Lewis or Brønsted acid, which activate the epoxide. A

good nucleophile then ring-opens the activated epoxide to form an alk-
oxide and CO2 is inserted to produce a carbonate. Finally, the intramo-
lecular ring-closing step provides the target cyclic carbonate, with
catalyst regeneration.
Bimetallic aluminum salen complex 1 (Fig. 1.1) was found to be an
excellent catalyst in the presence of tetrabutylammonium bromide
FIGURE 1.1 Aluminum salen and salphen complexes 1 and 2.
(TBAB) as a cocatalyst for this transformation at ambient temperature

and pressure.39 41 Typically, 2.5 mol% of aluminum complex 1 and
TBAB proved to be an effective catalytic system for a range of terminal
epoxides. Aluminum complex 1 is also able to catalyze the reaction
without the use of a cocatalyst, although harsher reaction conditions are
required.42 Subsequently, the formation of an unusual Al-carbonato spe-
cies, resulting from carbon dioxide insertion into one of the Al O bonds
of complex 1, was proposed and observed. Hence, a different reaction
mechanism for the transformation of epoxides into cyclic carbonates in
the absence of a cocatalyst was proposed.43 Later, a more active (com-
pared to complex 1) diamino aluminum salphen complex 2 was devel-
oped.44 In this case, 1.5 mol% of aluminum complex 2 and TBAB were
able to convert terminal epoxides and carbon dioxide into their corre-
sponding cyclic carbonates. Furthermore, aluminum complex 2 was also
active toward a range of internal epoxides, giving substituted cyclic car-
bonates in good to excellent yields.
Bimetallic aluminum salphen complex 3 was also shown to be an
effective catalyst for the production of various cyclic carbonates from
epoxides and carbon dioxide in the presence of TBAB (Fig. 1.2).45 The
reaction conditions (50 C, 10 bar carbon dioxide pressure) were slightly
harsher than those required for catalyst 1 and 2. Nevertheless, both ter-
minal and internal epoxides were transformed into their corresponding
cyclic carbonates using bimetallic aluminum salphen complex 3.
Mechanistic studies revealed that both aluminum centers were involved
in an intramolecular cooperative catalysis pathway. Interestingly,
monometallic aluminum salen complex 4 together with TBAB is a

FIGURE 1.2 Aluminum salphen and salen complexes 3 and 4.
suitable catalytic system for the kinetic resolution of epoxides through

enantioselective carbon dioxide coupling, giving the highest relative
rate of reaction for the two epoxide enantiomers (krel) of 15.4 and an
enantiomeric ratio (er) for the cyclic carbonates of 93:7.46
One-component aluminum salen complex 5 bearing appended pyri-
dinium salt substituents was shown to be an effective catalyst for the
coupling of epoxides and carbon dioxide (Fig. 1.3).47 The nature of the
FIGURE 1.3 Aluminum salen complexes 5 and 6.
cation proved to be important as decreasing the acidity of the pyridi-

nium salts decreases the catalyst activity. Similarly, aluminum salen
complex 6, which possesses intramolecular quaternary ammonium salts
as cocatalysts, was used in the regioselective ring-opening of epoxides
in a coupling reaction with carbon dioxide, affording cyclic carbonates
with complete retention of configuration.48 Notably, this catalyst system
exhibited nearly 100% regioselectivity for ring-opening at the methylene
C O bond for various terminal epoxides, such as styrene oxide and
epichlorohydrin, which contain electron-withdrawing groups. This pro-
vided access to various enantiopure cyclic carbonates that were hitherto
difficult to access.

Kleij and coworkers developed a class of well-defined aluminum

complexes derived from aminotriphenolate ligands, as shown in
Scheme 1.2.49,50 Complex 7 was shown to be highly active for cyclic
SCHEME 1.2 Reaction between 1,2-epoxyhexane and carbon dioxide catalyzed by

complex 7.
carbonate formation from epoxides and carbon dioxide (Scheme 1.2).

Initial experiments were carried out using 1,2-epoxyhexane as a sub-
strate and the reaction was examined at 90 C and 10 bar carbon dioxide
pressure. At a catalyst loading of 0.05 mol% and cocatalyst loading of
0.25 mol%, quantitative conversion to cyclic carbonate 8 was achieved
after 2 h, giving a turnover frequency (TOF) of 906 h21. In the presence
of 0.0520.1 mol% of aluminum aminotriphenolate complex 7 together
with tetrabutylammonium iodide as a cocatalyst, a range of highly func-
tionalized terminal epoxides could be transformed into their corre-
sponding cyclic carbonates in good to excellent yields (40%298%).49
Internal epoxides are widely considered to be very challenging sub-
strates for the formation of cyclic carbonates. However, the combination
of aluminum aminotriphenolate complex 7 together with tetrabutylam-
monium bromide as a catalyst system has proven to be most beneficial
for such transformation, using a very low catalyst loading of
0.120.5 mol%.50 Furthermore, a binary catalyst comprising a Lewis
acidic aluminum aminotriphenolate complex 7 and a nucleophilic cocat-
alyst, bis(triphenylphosphine)iminium chloride (PPNCl), is able to
mediate the challenging coupling of highly substituted cyclic and acy-
clic terpene oxides, and carbon dioxide into bio-based cyclic organic car-
bonates (Scheme 1.3).51 While cyclic terpene oxides exhibited excellent
conversion to the organic carbonate product with high diastereoselectiv-
ity, acyclic terpene oxides showed inferior chemoselectivity.
More recently, the binary aluminum aminotriphenolate complex 7
with PPNCl as cocatalyst has been reported to be a highly active sys-
tem for the conversion of fatty acid derived epoxides into their cyclic
carbonates under relatively mild reaction conditions (70 C285 C,
10 bar carbon dioxide pressure).52 More specifically, various mono-,
di-, and tris-epoxy substrates have been transformed into the corre-
sponding cyclic carbonates while maintaining high levels of

SCHEME 1.3 Reaction between terpene derived epoxides and carbon dioxide.
diastereoselectivity with cis/trans ratios of up to 99:1 in the cyclic car-

bonate products (Scheme 1.4).
SCHEME 1.4 Reaction between epoxidized methyl oleate and carbon dioxide.
Recent benchmarking studies among a series of aluminum-based

binary catalysts using different epoxides under various reaction condi-
tions demonstrated that binary catalysts 7/TBAB and porphyrin-based
complex 9/PPNCl (Fig. 1.4) display the highest catalytic activity.53
A series of aluminum(heteroscorpionate) catalysts have been devel-
oped for the formation of cyclic carbonates from epoxides and carbon
dioxide (Fig. 1.5).54 57 Generally, an elevated temperature and pres-
sure (50 C285 C, 10220 bar carbon dioxide pressure) were required
to convert both terminal and internal epoxides into their correspond-
ing cyclic carbonates. The effect of adding water to the reaction mix-
tures using complexes 10 and 11 was also investigated. It was found

FIGURE 1.4 Porphyrin aluminum complex 9 for the synthesis of cyclic carbonates.
FIGURE 1.5 Aluminum(heteroscorpionate) catalysts for cyclic carbonate formation.
that small amounts of water were beneficial for the catalytic activity,
increasing the conversion of styrene oxide to styrene carbonate.
However, a further increase in the amount of water added was detri-
mental and the conversion decreased due to hydrolysis of the alumi-
num alkyl groups.
Other reactions between epoxides and heterocumulenes (also known
as heteroallenes), such as carbon disulfide and isocyanates, afford cyclic
di- or trithiocarbonates and oxazolidinones, respectively, and these have
been studied using various aluminum-based catalysts (Scheme 1.5).
SCHEME 1.5 Reaction between epoxides and heterocumulenes.
These include aluminum complex 1,58 61 aluminum complex 7,62 and

aluminum heteroscorpionate complexes.63

1.2.2 Hydroelementation reactions

Hydrosilylation of alkenes and alkynes is one of the most effective and
convenient methods for the synthesis of organosilanes, which have great
versatility as building blocks in organic synthesis. A number of catalytic
systems, involving radical initiators,64,65 metal catalysts,66,67 and Lewis
acids,68,69 have been investigated for the addition of hydrosilanes to multi-
ple bonds. Yamamoto and coworkers reported the use of AlCl3 and trialkyl-
silanes for the hydrosilylation of alkynes, leading to cis-alkenylsilanes with
very high regio- and stereoselectivities in good to high yields.70 As a repre-
sentative example, 0.2 mol% of AlCl3 catalyzed the hydrosilylation of
1-dodecyne in the presence of 1.2 equivalents of triethylsilane at 0 C for
1 h, affording the corresponding cis-alkenylsilane in 95% yield (Scheme 1.6).
SCHEME 1.6 Lewis acid catalyzed hydrosilylation of 1-dodecyne with Et3SiH.
Similarly, Jung and coworkers investigated the hydrosilylation of cyclic

and linear alkenes with trialkylsilanes in the presence of Lewis acid catalysts
under mild reaction conditions, giving the corresponding trialkylsilylalkanes
in good yields.71 As an example, 0.2 mol% of AlCl3 was required at 0 C for
3 h for the hydrosilylation of 1-methylcyclohexene with Et3SiH to give cis-1-
triethylsilyl-2-methylcyclohexane in 74% yield, consistent with a trans-hydro-
silylation pathway. The authors suggested that the reaction proceeds by the
formation of a silylenium ion Et3 Si1 AlCl2 4 from AlCl3 and the silane,
which then adds to the alkene to generate a carbocation (Scheme 1.7).
SCHEME 1.7 Proposed reaction mechanism for the hydrosilylation of 1-methylcyclohexene.
Recently, well-defined aluminum species have been investigated for the

hydrosilylation of unsaturated carbon carbon bonds. Chen and coworkers
isolated and fully characterized a frustrated Lewis-pair catalyst for the
hydrosilylation of unactivated alkenes by mixing an excess of Et3SiH with

Al(C6F5)3 in hexane.72 With the super Lewis acidity of Al(C6F5)3, the sila-
ne alane system exhibits high catalytic activity. Indeed, 98% conversion
during the hydrosilylation of 1-hexene was achieved using 5 mol% of sila-
ne alane complex [Et3SiH_Al(C6F5)3] in 30 min, with a TOF value of 39 h21
(Scheme 1.8). Noticeably, the silane borane complex [Et3SiH_B(C6F5)3],
SCHEME 1.8 Hydrosilylation of 1-hexene using silane alane complex.
a superior catalyst for hydrosilylation of carbonyl substrates, showed a

much slower catalytic activity for 1-hexene with TOF 5 1.5 h21.
Nikonov and coworkers reported the use of [AlH(nacnac)][B(C6F5)4]
(nacnac 5 CH{C(Me)N(2,6-iPr2C6H3)}2) 15 for alkene hydrosilylation.73
Using 1 or 5 mol% of catalyst 15 in the presence of Et3SiH, a range of
terminal alkenes and cyclohexene all showed quantitative conversion to
the alkylsilanes in less than 10 min at room temperature. Complex 15 is
also effective in catalyzing the hydrosilylation of aliphatic alkynes at
room temperature albeit with much longer reaction times of 24 h.
Despite the observed high conversion to the hydrosilylation products
for both alkenes and alkynes, the isolated yields for the target silanes
were rather low due to formation of redistribution products.
Mechanistic studies suggest that Lewis acid activation by the cationic
aluminum center was involved in the process (Scheme 1.9).
SCHEME 1.9 Proposed mechanism for complex 15 catalyzed hydrosilylation.

Roesky and coworkers showed that the well-defined aluminum dihy-

dride LAlH2 (L 5 CH(CMeNAr)2, Ar 5 2,6-Et2C6H3) 16 (3 mol%) was
able to catalyze the hydroboration of terminal alkynes with HBpin
(pinacolborane) at 30 C for 12 32 h (61% 82% yields), affording the
trans-vinylboronate ester arising from the anti-Markovnikov addition of
the borane (Scheme 1.10).74 Quantum mechanical calculations indicate
SCHEME 1.10 Hydroboration of alkynes catalyzed by aluminum catalysts 16 and 17.
that the alkyne is activated by the catalyst, leading to the formation of

an aluminum acetylide intermediate. In comparison, the catalytic activ-
ity of the N-heterocyclic imine-substituted aluminum hydride 17 toward
the hydroboration of terminal alkynes is inferior, requiring a higher
temperature (80 C) and extended reaction time of 40 h to produce high
conversions (Scheme 1.10).75
More recently, Cowley and coworkers developed a catalytic system
based on either the commercially available aluminum hydride DIBAL-H

(iBu2AlH) or bench-stable Et3Al DABCO (DABCO 5 1,4-diazabicyclo
[2.2.0]octane) (10 mol%) and HBpin, which was efficient for alkyne
hydroboration (Scheme 1.11).76 In the presence of HBpin (1.2 equivalents)
SCHEME 1.11 Hydroboration of alkynes catalyzed by DIBAL-H.
at 110 C for 2 h in toluene, a series of functionalized and unfunctiona-

lized alkynes was hydroborated in 40% 2 89% yields.
Notably, the addition of the HsB bond is chemoselective to the
alkynes in the presence of alkenes. Both DIBAL-H and Et3Al DABCO
showed equal catalytic activity across all substrates tested, which
strongly suggests a shared mode of operation. The reaction mechanism
is thought to be different from that with aluminum dihydride complex

16. A series of mechanistic studies revealed that the hydroboration pro-

ceeds through initial hydroalumination, followed by σ-bond metathesis
with HBpin, where the alkenyl substituent undergoes transmetallation
from aluminum to boron, thus regenerating the aluminum hydride
(Scheme 1.12).
SCHEME 1.12 Proposed mechanism for aluminum hydride catalyzed hydroboration.
Similarly, Cowley and coworkers also demonstrated the use of com-

mercially available aluminum hydrides for the hydroboration of
alkenes.77 Thus by using 10 mol% of LiAlH4 and 1.2 equivalents of
HBpin, the hydroboration of alkenes can be performed at 110 C in 3 h,
giving the linear boronic ester in excellent yields with a regioselectivity
of 99:1 over branched products.
Bergman and coworkers described well-defined four coordinate alu-
minum complexes bearing a dianionic phenylene-diamine-based ligand,
which were active in the intramolecular hydroamination of aminoalk-
enes (Scheme 1.13).78 Specifically, aluminum complex 18 (10 mol%) was
SCHEME 1.13 Hydroamination of aminoalkenes catalyzed by complex 18.
able to promote the hydroamination of primary aminoalkenes bearing

geminal substituents on the backbone to give 5- and 6-membered rings
in moderate to good yields, when performing the reaction at 150 C over
extended reaction times. It was proposed that the reaction mechanism
involved an Al-NMe2/H-NHR metathesis pathway to give an

aluminum olefin-amide species, followed by cyclization with the pen-

dent olefin group.
Wehmschulte and coworkers investigated cationic dialkylaluminum
and m-terphenylalkylaluminum compounds as catalysts for the intramo-
lecular hydroamination of primary and secondary aminopentenes
(Scheme 1.14).79 It was found that reaction rates were dependent on the
SCHEME 1.14 Aluminum catalyst for the hydroamination of primary and secondary
aminopentenes.
substrate and the catalyst substituents. The most sterically hindered spe-
cies 19 was the most active of the catalysts tested. Thus using 10 mol%
of catalyst 19 at 135 C afforded the targeted pyrrolidines in good yields
over a short reaction time (0.2521.5 h).
Duñach and coworkers reported the use of aluminum trifluoromethane-
sulfonate, Al(OTf)3, as an efficient catalyst for the intramolecular hydroalk-
oxylation of unactivated alkenes.80,81 The reaction can be performed in the
presence of 5 mol% of Al(OTf)3 under mild conditions with a range of
γ,δ-unsaturated alcohols, leading to the corresponding tetrahydrofurans and
tetrahydropyrans in high yields with Markovnikov regioselectivity (Scheme
1.15). The reaction mechanism is said to proceed via Lewis superacid-type
SCHEME 1.15 Hydroalkoxylation of 2-allylphenol catalyzed by Al(OTf)3 and Al(OiPr)3.

catalysis. Similarly, William and coworkers also reported the intermolecular

hydroalkoxylation of alkenes catalyzed by Al(OTf)3.82 More recently,
Hintermann and coworkers described the use of aluminum iso-propoxide,
Al(OiPr)3, as a catalyst for the hydroalkoxylation of 2-allylphenols.83 In con-
trast to the reaction conditions reported by Duñach and coworkers, drastic
reaction conditions were required to achieve similar conversions of the tar-
get products. The reaction tolerates a number of functional groups, such as
halogens, methoxy, and cyano. However, substrates capable of forming
stable chelates with aluminum(III), such as 6-methoxy- and 6-formyl-
substituted allylphenols, and benzylic alcohol could not be cyclized.
1.2.3 Polymerization reactions

In the past decades, alkyl and alkoxide aluminum complexes have been
developed as catalysts for the ROP of cyclic esters.84 88 In particular, alu-
minum alkoxide complexes generated in situ from the reaction of an alkyl
aluminum complex with an alcohol have been successfully used for the
stereoselective ROP of rac-lactide (rac-LA), affording stereoenriched poly-
lactides (PLA). The stereoselectivity is determined by the presence of a
chain-end control mechanism or a site control mechanism.86 88 In general,
the ROP of cyclic esters catalyzed by aluminum complexes occurs via a
coordination insertion mechanism (Scheme 1.16). In the first step, the
SCHEME 1.16 Ring-opening polymerization of cyclic esters.
monomer coordinates to the aluminum center. Then, the nucleophile ring-

opens the activated monomer affording an aluminum alkoxide complex
that can undergo successive ring-opening reactions of cyclic esters to afford
the desired biodegradable polyester materials.
The coordinated ligands on the aluminum center have a great effect on
the catalytic activity since they allow the fine-tuning of the electronic and ste-
ric properties and stability of the resulting aluminum complexes. A broad
range of ligands have been used for the preparation of aluminum complexes
that act as catalysts for the ROP of cyclic esters. Salen and related ligands are

among the most studied ligand precursors for the synthesis of aluminum cat-
alysts due to their straightforward synthesis from an aldehyde and a diamine
and their high versatility as they allow the facile modulation of the steric and
electronic properties.89 In 2010 Darensbourg reported the use of chiral and
achiral half-salen aluminum complexes for the stereoselective ROP of rac-
LA.90 All complexes were found to be catalytically active in toluene at 70 C,
providing PLA with experimental molecular weights close to the theoretical
values, narrow polydispersity index (PDI) and a Pm value (isotactic selectivity
as defined by the probability of meso linkages, as determined by NMR) up to
0.76, indicating that these complexes catalyze the stereoselective ROP of rac-
LA. These studies were extended to investigate the ROP of trimethylene car-
bonate (TMC), δ-valerolactone (δ-VL), rac-β-butyrolactone (rac-β-BL), and
ε-caprolactone (ε-CL), using complex 20 as catalyst, obtaining the correspond-
ing polycarbonates or polyesters (Fig. 1.6).91 A detailed kinetic study con-
FIGURE 1.6 Aluminum complex 20 for the ROP of cyclic esters.
firmed that the ΔG‡ values are in the order rac-LA rac-β-BL .
δ-VL . TMC ε-CL. The ROCOP of rac-LA and δ-VL provided a tapered
polylactide polyvalerolactone copolymer due to the higher reactivity of the
catalyst toward the rac-LA unit over the δ-VL monomer.
Salen alkyl aluminum complexes were developed as highly stereoselec-
tive catalysts for the stereoselective ROP of rac-LA at 70 C in toluene, pro-
ducing quasi-isotactic PLAs, (Pm 5 0.94 0.97) at high conversions with
narrow PDIs (Scheme 1.17).92 The high crystallinity of the polymer was
SCHEME 1.17 Stereoselective ROP of rac-LA catalyzed by complex 21.

confirmed by its high melting point (Tm) of 205 C. Salen and salan alumi-
num complexes have also been used as catalysts for the ROP of rac-β-BL,
forming high-molecular-weight polyhydroxybutyrate (PHB).93 It is impor-
tant to note that these complexes catalyze the immortal ROP of rac-β-BL
since the addition of an excess of benzyl alcohol (BnOH) did not have a
detrimental effect on the catalytic activity. Gradient copolymers with nar-
row polydispersities could be obtained when the ROCOP of rac-LA and
rac-β-BL was performed in toluene at 85 C.
Aluminum salalen complexes were investigated as catalysts for the
homo- and copolymerization of L-, D-, rac-, and meso-LA and ε-CL.94 As
expected, the homopolymerization of L- and D-LA afforded isotactic
PLLA and PDLA, respectively, while the ROP of rac- or meso-LA pro-
duced isotactic- or heterotactic-enriched PLAs, respectively. The
ROCOP of L-LA and ε-CL was studied, obtaining random copolymers
with very similar average lengths of the caproyl and lactidyl units.
Thomas and coworkers reported on the mechanism for the ROP of rac-
LA at room temperature using a highly efficient salen chloride aluminum
catalyst in combination with PPNCl in propylene oxide as solvent.95 The
proposed mechanism involves the formation of salen aluminate species
by two different pathways (Scheme 1.18). The salen chloride aluminum
SCHEME 1.18 Formation of salen aluminate species in the ROP of rac-LA at room
temperature.

complex can react with PPNCl to form the bis-chloride aluminate species
4a that can react with two molecules of epoxide to form a six-coordinated
bis-alkoxide aluminate species 4c, which is in equilibrium with the
mono-alkoxide species 4d and PPNOR. Density functional theory (DFT)
calculations were performed to study the origin of the high catalytic
activity displayed by this catalyst system. It was concluded that the
extraordinary performance is due to the formation of external nucleo-
philic alkoxide, which decreases the energy barrier for the ring-opening
of the lactide monomer by 5.7 kcal mol21.
Aluminum complexes containing a range of N,O ligands have been
designed and used as catalysts for the ROP of cyclic esters. Phenoxyimine
alkyl aluminum complexes in combination with BnOH cocatalysts displayed
high catalytic activity toward the ROP of rac-LA,96 the ROP of rac-β-BL,97
and ROCOP of L-LA and rac-β-BL.97 The use of a bulky o-SiPh3 substituent
in the phenoxy moiety allowed the synthesis of a stereoselective ROP cata-
lyst, obtaining PLA with Pm up to 0.80 and good control over the molecular
weight of the polymer and narrow polydispersities.96 Milione and cowor-
kers have used phenoxyimine aluminum catalysts for the ROP of rac-β-BL
in toluene at 100 C obtaining PHB with medium to high molecular weight
and narrow PDI.97 The ROCOP of L-LA and rac-β-BL was also studied using
100 equivalents of both monomers, obtaining random copolymers with a
glass transition temperature (Tg) of 31 C.97 Five-coordinated salicylbenzoxa-
zole aluminum complexes were used as catalysts for the ROP of rac-LA and
ε-CL, obtaining the corresponding polyesters with molecular weights close
to the theoretically predicted values and narrow PDIs.98 Interestingly, these
complexes catalyzed the stereoselective ROP of rac-LA, obtaining PLAs with
Pm 5 0.64 2 0.75, which is higher than the Pm achieved by the corresponding
four-coordinated aluminum analogs (Pm 5 0.54 2 0.70).
Carpentier et al. developed a range of fluorinated alkoxyimino alumi-
num complexes for the ROP of rac-LA (Scheme 1.19).37,99 The use of
SCHEME 1.19 ROP of rac-LA catalyzed by fluorinated alkoxyimino aluminum complexes.

dialkylaluminum complexes, {ON}AlMe2, in combination with BnOH

produced essentially atactic PLAs.99 However, when a bridge between
the two alkoxyimino moieties was used, isotactic-enriched PLAs were
obtained with Pm between 0.78 and 0.87 due to the higher conforma-
tional rigidity.37
Aluminum complexes supported by β-ketiminato ligands were devel-
oped by Li and coworkers.100,101 These complexes very efficiently cata-
lyzed the ROP of ε-CL and L-LA in the presence of isopropyl alcohol
(iPrOH) as a cocatalyst, giving 94% conversion for the ROP of 1000
equivalents of ε-CL in 30 min and complete conversion of 100 equiva-
lents of L-LA in 1 h at 80 C.100 Block and gradient copolymers of ε-CL
and L-LA could be obtained with the most active catalyst. In an exten-
sion of this work, quasi-random copolymers of ε-CL and L-LA could be
prepared by modifying the β-ketiminato ligand.101 The copolymers
obtained showed similar average lengths of the caproyl and lactidyl
sequences and reactivity ratios of the two monomers of rLA 5 1.31 and
rCL 5 0.99, confirming the essentially random copolymerization of the
two monomers. A range of copolymers with different thermal proper-
ties were obtained by variation of the ε-CL:L-LA ratio.
Random copolymers of ε-CL and rac-LA were prepared by using pyr-
rolylpyridylamido aluminum catalysts in toluene at 70 C using iPrOH
as cocatalyst (Scheme 1.20).102 The reactivity ratios obtained for each
SCHEME 1.20 Preparation of random copolymer PCL PLA catalyzed by complex 24.
monomer were close to 1, indicating a random copolymerization. In all

cases, amorphous materials were obtained with Tg values from 246 C
to 30 C.
Otero and coworkers have reported several families of scorpionate
aluminum complexes as catalysts for the formation of polyesters by
ROP and ROCOP of rac- or L-lactide and/or ε-caprolactone and epox-
ides with cyclic anhydrides.103 108 The molecular weight, molecular
weight distribution, and tacticity of the homopolymers and copolymers
obtained could be modulated by changing the design of the scorpionate
ligand (Scheme 1.21). For the ROP of cyclic esters, the aluminum

SCHEME 1.21 Scorpionate aluminum complexes for the ROP and ROCOP of cyclic
esters.
complex did not require the presence of a cocatalyst to perform a living

polymerization. Interestingly, complex 25 allowed the preparation of
cyclic polycaprolactones instead of a linear PCL via ring-expansion
polymerization (Scheme 1.21).
1.3 Iron-based catalysts
Transition metals are widely used in catalysis to promote a broad

range of chemical transformations.109 The use of iron catalysts in
organic synthesis is a huge field of interest. Iron catalysts have been
used in Alder-ene-type, addition, annulation, cross-coupling,110 cycliza-
tion, cycloaddition, domino, elimination, (de)hydrogenation,31 hydrome-
talation,111 isomerization, metathesis, oxidation, polymerization,
rearrangement, reduction,111,112 and substitution reactions (amongst
others).113 Iron is a nontoxic, air-stable, and inexpensive metal, which
is readily abundant across the globe, environmentally benign, and plays
an important part in numerous biological catalytic systems.114 Iron is
therefore an ideal transition metal in terms of Green Chemistry

principles115 and sustainability, compared to traditionally used transi-

tion or precious metals.116 In this section, only iron-catalyzed cross-cou-
pling (i.e., CsC bond formation), CsX heteroatom bond formation,
polymerization and dehydrogenation reactions will be discussed, with a
focus on research reported over the last 15 years. This review will not
give a comprehensive review of all reported procedures but hopes to
give a flavor of iron-catalyzed reactions. For those seeking more in-
depth background information on iron-catalyzed reactions, readers are
encouraged to consult the following reviews.31,110 114,116 132
1.3.1 Cross-coupling reactions

Cross-coupling reactions occur when two reagents, both with activat-
ing groups, react together with a metal catalyst to form a new covalent
bond, driven by loss of the activating groups. Iron cross-coupling reac-
tions were first reported in the 1940s by Kharasch and Fields, when
investigating the reaction of Grignard reagents with organic halides in
the presence of metallic halides.133 Iron cross-coupling was then studied
thoroughly and brought to the forefront by Kochi and Tamura in the
1970s,134 136 which led to a vital turning point for iron-catalyzed cross-
coupling reactions and iron catalysis in general, when they reported the
alkenylation of alkyl Grignard reagents with vinyl bromides using Fe
(III) chloride (Scheme 1.22).136
SCHEME 1.22 Iron-catalyzed alkenylation of alkyl Grignard reagents with vinyl

bromides.
Although iron-catalyzed cross-coupling reactions preceded palla-

dium- and nickel-catalyzed reactions, interest waned until the start of
the millennium,113 when it again increased especially with a view to
formation of CsC bonds in pharmaceuticals128 and natural products.
Iron-catalyzed cross-coupling reactions include CsX/C metal cross-
coupling, CsC bond formation by CsH bond activation,129 and decar-
boxylative and decarbonylative coupling reactions.113 Those interested
in these iron-catalyzed cross-coupling reactions are recommended to
read the following articles.110,118 121,128,132
Perhaps one of the most important iron catalysts used in cross-
coupling reactions for pharmaceutical128 and natural product synthesis
is tris(acetylacetonato)iron(III) (Fe(acac)3) (Scheme 1.23A D). In 2008 a

SCHEME 1.23 Pharmaceuticals, natural products, and vital compounds that have been
synthesized using Fe(acac)3.137,139 141
key synthetic step in making the anticancer agent Combretastatin A-4

was achieved using Fe(acac)3 (Scheme 1.23A).137 That same year, a route
to the immunosuppressive agent FTY720 was devised by reacting octyl
magnesium bromide with an aryl triflate and Fe(acac)3.138 A more
recent alternative route was reported by Feng in 2012, via an iron-
catalyzed cross-coupling reaction between methyl 4-chlorobenzoate and
octyl magnesium bromide (Scheme 1.23B).139 In 2012 the perfume ingre-
dient and dusk musk odorant (R,Z)-5-muscenone, aka Muscenone, was
synthesized via a cross-coupling reaction with Fe(acac)3 (Scheme
1.23C).140 Also in 2012, iron-catalyzed aryl alkyl cross-coupling reac-
tions were used to synthesize nine examples of pentapodal ω-functional
derivatives of corannulene, important building blocks for synthesis and
supramolecular chemistry, in good to high yields (Scheme 1.23D).141
Besides the iron catalyst Fe(acac)3, other simple iron-based salts, such
as FeF2, FeF3, FeCl2, FeCl3, FeBr2, FeBr3, and Fe(OAc)2, have been used
in cross-coupling reactions.113 There has also been success in using
more well-defined iron complexes as catalysts in cross-coupling reac-
tions (Scheme 1.24A C). In 2013 Bedford et al. reported that iron

SCHEME 1.24 Iron complex-catalyzed cross-coupling reactions.142 144
phosphine catalysts 26 and 27 could perform cross-coupling reactions

over a broad substrate scope in superb yields (Scheme 1.24A).142 The
year prior, Deng et al. reported that dinuclear iron complex 28 could
successfully cross-couple primary alkyl fluorides with aryl Grignards
(Scheme 1.24B).143 In 2013 iron(III)amine-bis(phenolate) complex 29 was
reported by Kozak et al. in the cross-coupling of benzyl halides (Scheme
1.24C).144 Success in using iron salen145 and iron(III) amine-bis(pheno-
late)146 complexes for these reactions has also been reported.
1.3.2 C heteroatom bond forming reactions

CsX heteroatom bond formation is another area of huge interest for
iron-catalyzed reactions. Carbon heteroatom bonds are important com-
ponents in many organic compounds used in pharmaceutical and bio-
logical research.116 Iron catalysis has been successfully employed in

forming CsN, CsO, and CsS bonds via N-arylation, hydroamination,

aziridination, allylic amination, addition, O-arylation, CsH oxidation,
alkene oxidation, rearrangements, S-arylation, and Michael addition116
(some examples are shown in Schemes 1.25 and 1.26).116 Those
SCHEME 1.25 Iron catalyzed CsN, CsO, and CsS bond formation.148 151
SCHEME 1.26 Synthesis of methanol using iron scorpionate complex 32.
interested in XsX heteroatom formation reactions are advised to consult

Bolm’s 2008 and Melen’s 2016 reviews.116,147 In 2018 Bernskoetter
reported the iron-catalyzed N-formylation of amines (CsN bond forma-
tion) using iron pincer catalyst 30 (Scheme 1.25A).148 This catalyst was

compatible with a broad range of substrates and reactions only

required 0.02 mol% of complex 30. Imines are another interesting class
of compounds, as they are used in pharmaceutical, dye, polymer, and
pigment syntheses. In 2017, Milstein used iron pincer complex 31 to
produce secondary aldimines via a hydrogenative cross-coupling reac-
tion between nitriles and amines (Scheme 1.25B).149 This reaction could
be performed under mild conditions with numerous nitriles and
amines, and was the first ever metal catalyst reported to perform this
reaction. In 2008 Bolm et al. reported that the simple iron salt FeCl3
(when .98% pure) could be used to generate CsO and CsS bonds, by
reacting aryl iodides with phenols150 and aromatic thiols,151 respectively
(Scheme 1.25C and D).
In 2017 the iron scorpionate complex 32 was reported to convert car-
bon dioxide and hydrogen into methanol via a selective reductive ami-
nation/hydrogenative cross-coupling reaction (Scheme 1.26).152 This is a
reaction of huge interest, as not only does the conversion of carbon
dioxide into methanol provide the opportunity to reduce carbon dioxide
emissions, but it also recycles this “waste” gas into an alternative fuel,
fuel additive, and intermediate in the production of, for example, plas-
tics, paints, and textiles.153 This reaction required no solvent, an
extremely low catalytic loading of 32 and was the first ever report in the
literature of a scorpionate catalyst accomplishing this reaction. The use
of pentaethylenehexamine (PEHA) was required to increase the yield of
methanol from 28% to 46%, but the reaction could be performed under
amine free conditions if desired. Catalyst 32 can be made via a simple
one-pot process, making this catalyst extremely green. While the mecha-
nism of this reaction remains unknown,152 this work is extremely inter-
esting as the substitution of rare or precious metal catalysts with iron
species is often problematic and does not result in active catalysts.154
Alternative routes to CsX (as well as CsC) bond formations are via
CsH activation or transformation reactions,114,129 which were first
reported by Nakamura et al. in 2008.155 In the decade following this dis-
covery, numerous iron catalysts have been used in CsH activation reac-
tions, with many of these catalysts requiring only low temperatures and
often giving quicker conversions than the equivalent palladium, ruthe-
nium, and rhodium catalysts.129 Reactions such as CsH bond amina-
tion, borylation, silylation, and tritiation have all been performed using
iron catalysts (Scheme 1.27).129 Tritiation reactions are particularly inter-
esting and are vital in drug research, as converting a CsH bond into a
CsH3 bond (tritium labeling) enables the pharmacokinetics and phar-
macodynamics of new drug candidates to be studied.156 In 2016 Chirik
et al. reported the ability of iron catalyst 34 to label the calcimimetic
drug Cinacalcet,157 which is used to treat hyperparathyroidism (overac-
tive functioning of the parathyroid glands) during the end-stages of

SCHEME 1.27 Iron catalysts reported in the formation of CsN, CsSi, and Cs3H
157,159,160
bonds.
renal disease (Scheme 1.27C).158 The tritium labeling ability of catalyst

34 was comparable to the state-of-the-art iridium catalyst (Crabtree’s
catalyst), which requires dichloromethane as the reaction solvent to
function.157
Iron-catalyzed radical reactions can also form CsX bonds via CsH
bond halogenation and oxidation via Gif or Fenton chemistry.129 Those
interested in these processes are recommended to read the articles by
Barton,161 Tapper,162 and Sawyer.163
1.3.3 Polymerization reactions

Iron complexes have been used as catalysts for a range of polymeri-
zation processes.164 169 In this section, recent advances on the ROCOP

of epoxides and CO2 to afford polycarbonates and the ROCOP of epox-

ides and cyclic anhydrides to produce polyester materials catalyzed by
iron complexes will be described (Scheme 1.28).
SCHEME 1.28 ROCOP of epoxides with CO2 or cyclic anhydrides.
In 2011 Williams et al. reported the first example of an iron catalyst

for the reaction of epoxides and CO2 to afford either cyclic- or polycar-
bonates.170 In this contribution, the bimetallic air-stable Fe(III) complex
36 catalyzed the production of poly(cyclohexene carbonate) (PCHC) at
80 C with high selectivity (Scheme 1.29). The catalyst was found to be
SCHEME 1.29 Synthesis of poly(cyclohexene carbonate) catalyzed by complex 36.
active even at 1 atm of CO2 pressure providing a copolymer in 93%

yield but with only 66% of carbonate linkages. However, when the reac-
tions were carried out at 10 atm of CO2 pressure, PCHC was obtained
with selectivities greater than 99% and no trans-cyclic carbonate

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This village, like so many others, is divided into two sections, each
of which has its dubu. At these annual festivals only one division
dances, the members of the other being spectators. If, for some
reason, such as the death of an important man, a challenge is not
taken up, there will be no dance the following year, which is a local
misfortune.
A man of the other division stepped forward and picked up the
areca nut; then those on the dubu broke up the bunches of the nuts
and threw them among the spectators for a scramble, and a scene of
hilarious excitement began. I joined in the scramble, and secured
one or two nuts.
Fig. 25. Irupi Dance, Babaka
Shortly after this seven recently tattooed girls walked in a row up

and down the broad open space in the village in front of the dubu.
The irupi or iropi dance was to be performed by them, and the pigs
for the feast had been provided by their relatives. The girls walked in
a somewhat stately manner, and gracefully swung a cord of about
three feet in length, to which a small netted bag was attached; the
other end of the cord was attached to the waist-belt of the petticoat
at the back. They swung it with the right hand, causing it to make a
graceful sweep behind the back round to the left side, where it was
caught by the left hand. During this manœuvre the whole body made
a half turn. The action was then repeated with the left hand, the
tassel being caught with the right hand. Up and down the little
damsels walked, well pleased with themselves, and fully conscious
that they were the centre of attraction; it was an elegant dance, and
really quite charming. During the irupi dance some women sat on the
dubu and beat the drums; this is the first time I have anywhere seen
women beating drums, and it is only on this occasion that women
may mount on a dubu. The movements of the girls were regulated by
the staccato beats of the drums.
The same girls next ascended the dubu and stood in a row facing
the village square. Two men then carried the pig, which was tied on
to a pole, and stood in front of the girls. An old woman came and
stood beside them; she was not ornamented in any way, whereas
the girls wore numerous swagger petticoats; round their necks were
as many necklaces and ornaments as they could muster, and some
had wonderful shell head-dresses. The girls next took off all their
petticoats and were anointed by the old woman, who dabbed each
girl with a mixture of coconut oil and water by means of a bunch of
wild thyme. As soon as the anointing was completed a drum was
beaten, and the girls quickly dressed themselves and jumped down
from the dubu. This ended one of the most interesting ceremonies it
has been my lot to witness.
It is evident that the latter part of the ceremony is the most
important, and that it is a fertility ceremony. I was told that it brought
good luck to the plantations. It is interesting to note that here, as in
India, and indeed in many parts of the world, the ceremony for
ensuring a bountiful harvest is performed by the women.
The next day the pig was killed for the feast, and there was
renewed dancing.
PLATE XIV
GIRLS OF BABAKA DRESSED FOR THE ANNUAL CEREMONY
GIRLS ON THE DUBU AT BABAKA FOR THE ANNUAL

CEREMONY
Mr. R. E. Guise, who has resided for over ten years in the Hood
peninsula, has recently described this ceremony in the Journal of the
Anthropological Institute (xxviii., 1899, p. 215). Apparently the
second and principal part of the ceremony (kuiriga) was somewhat
abbreviated on the occasion when we witnessed it. As soon as the
girls on the dubu have thrown their petticoats behind them, married
women advance and place in front of each girl a basket containing a
quantity of areca nuts, on the top of which are a few yams and a
small knife. After the anointing, each girl takes a yam in her left hand
and the knife in her right, and at each beat of the drum cuts off a
piece of the yam, bends her knees, and slightly bows her head,
causing the weighted head-dress to sway forwards. The whole effect
is described as being wonderfully pretty. After each girl has cut up
half a dozen yams the female orchestra give two sharp taps, and the
drums cease beating. The girls immediately take up the baskets and
pelt the crowd with the areca nuts; this part of the affair is much
appreciated by the onlookers, who scramble for the nuts, tumbling
over one another like children.
The girls quite enjoy the position, and do not show any shame.
Very few, if any, men seem to care to look on the ceremony, old
women, widows, and married women who have daughters
constituting the majority of the bystanders.
I had previously known about this ceremony and understood that it
was of an indecent character, but my experience quite corroborates
these statements of Mr. Guise. I must confess to feeling surprised
that the men took no notice at all of the girls, and it was perfectly
evident that this was regarded by them as solely a woman’s
ceremony.
One day we started in the early morning to visit Keapara
(Kerepunu). Mr. A. C. English, the Government Agent for the Rigo
District, had followed us to Bulaa, and he took us in his whale-boat.
After rowing for a long time in a heavy sea against a head wind Mr.
English found that the wind and tide were too strong for us to cross
Hood Bay; so the sail was set, and we ran down the bay to Kalo. To
windward of the mouth of the Vanigela is a sand-bar, which deepens
as it projects into the bay, and over this the breakers came rolling in
with any amount of surf and flying spray. We had a few anxious
moments as the boat was carried along through the seething water,
but we got safely through into the quiet water beyond, and then rode
into the mouth of the river, a vision of fairy calm and beauty. Nipa
palms erected their rigid fern-like leaves directly from the water; they
were banked by varied tropical foliage, and shooting skywards were
the slender white stems of the coconut palms with their waving leafy
crowns.
After a short spell we walked for eight miles along the sand beach
round the bay till we came to the entrance of Hood lagoon, over
which we were ferried in a canoe, and on arriving at Keapara we
were hospitably received by Tau and his wife, the L.M.S. South Sea
teacher, who gave us afternoon tea before we visited the village.
The sand beach in front of the village presented a busy scene;
until now I had not come across such activity as was here displayed.
Several canoes were being made, and not only was there a
continuous succession of chopping noises, but the sense of smell
was also affected, partly by the smoke of the fires, but mainly by the
very disagreeable odour given out by the soft wood as it is chipped
by the adzes.
The trees of which the canoes are made grow up the Vanigela
River; they are cut down, and their trunks are floated down the
stream to its mouth. The Kalo men sell the lumber to the Keapara
men, who tow it to their village. The outside of the canoes is cut with
steel tomahawks obtained from the white man, but the logs are
hollowed out with stone adzes, the stone blade of which can be
shifted round to any angle by turning the holder on the shaft. It
seems strange that these primitive shipwrights should prefer stone
implements to iron ones for hollowing out the canoes; perhaps it is
because they are frightened lest the sharper iron blade should
inadvertently cut through the thin side of the hull. After the canoes
are dug out and trimmed down they are charred by fires lit outside
and inside them; the effect of this is to harden the wood, and I
suppose to somewhat fill up the pores so as to make the craft more
seaworthy. I believe that one result of applying fire to the canoes is
to make them open out more widely. Probably in precisely the same
manner, save that no metal tool was available, our Neolithic
ancestors manufactured their canoes. It was an unexpected
pleasure to have this glimpse into the Stone Age.
PLATE XV
HOLLOWING OUT A CANOE WITH STONE ADZES AT KEAPARA

A BULAA GIRL BEING TATTOOED
Sitting on the sand beach was a man chipping out a wooden bowl
from a piece of the same kind of wood as that of which the canoes
were made. He employed a small adze, constructed on the same
principle as that of the large adzes used in canoe making. In this
instance the blade was made of iron, but so fashioned as precisely
to resemble the original stone blade; subsequently I procured a small
stone adze. We photographed the man at work, and, as we have
experienced often, he took no notice of us; but he appeared to be
much surprised when I bargained for his implement and the
unfinished bowl. A native cannot in the least understand why one
wants to purchase an unfinished article and the tool with which it is
being made.
The Keapara natives buzzed round us like flies, offering for sale
“curios” of all kinds and sea shells; often the former were broken and
worthless specimens. One did not know which way to turn, so
persistent were they, and the din was deafening. Well did they
maintain their reputation for being keen, and whenever possible,
unprincipled traders; still we did very well and got our things
reasonably enough. I understand that they live principally by barter,
not only locally, but also doing some trading up and down the coast.
Next morning we paid a visit to the adjoining fishing village of
Alukune, or Harukune, which is situated on the other side of the point
of land on which Keapara stands. The natives, as is usually the case
with fisher-folk in Europe, keep very much to themselves, but here
they have good reason for this aloofness. The more powerful
Keapara men have for generations been in the habit of levying toll
from them in the shape of fish and other marine produce. The
Alukune possessed no land, and were not allowed to acquire any,
though the Keapara had more than enough for their own wants.
Vegetable food being a necessity, the Alukune women either had to
go to Kalo for it or had to buy it from their Keapara neighbours,
giving fish in exchange, but the latter, being the stronger tribe, were
able to obtain the fish at a very cheap rate. They were not only
oppressed in this and other ways, but their women were seized and
taken as wives by Keapara men. Some thirty-eight years ago half the
village, driven to desperation by the oppressions of their neighbours,
left in a body and settled at Hood Point, and built the village of Bulaa.
The other half who remained were still held in subjection by
Keapara, and their condition was but little improved since the old
days until very recently, and even now they do not appear to be in a
happy or thriving condition.
Although the inhabitants of Alukune are fisher-folk, they obtain
their canoes from Keapara, and in return they have to pay half the
catch; in other words, they have to trade on the half-profit system.
We obtained very little in this village, but I cut some samples of
children’s hair, to the amusement of the unlocking crowd and to the
great perplexity of the children themselves. The children were
playing with toy miniature bows and arrows made from the mid-ribs
of palm leaflets.
Just before we started in the whale-boat English arrested a man
for petty larceny, and we had an exhibition of native grief. Men and
women rushed up to the prisoner as he was being handcuffed and
led off to the boat, rubbing noses and applying their mouths to his
cheek, but I did not hear any actual kissing. On all sides was
weeping and wailing; many clawed the sides of their heads and
faces either on one or both sides; some beat their heads and faces,
clasped hands were wrung alternately on each side of the head at
the level of the ear, frequently the clasped hands were held at the
back of the head. There was a great deal of tragedy for very little
cause, as the man was going for only a week’s imprisonment, or
rather a week of forced labour on roadmaking. The comic element
was that he had picked a policeman’s pocket.
We had a spanking sail across the bay, and had a second
breakfast on our arrival soon after eleven. About 12.30 Wilkin and I
walked over to Babaka to take some more photographs. Ray worked
that afternoon at languages, and Seligmann had a very profitable
time testing the keenness of the eyesight of the natives.
During the next few days we got through a fair amount of
anthropological measurements and other work. We persuaded some
girls to demonstrate the process of tattooing, which we
photographed. The girl to be tattooed lay on the ground, and the
operator held a special clay vessel in one hand, in which was a black
fluid paste made from burnt resin; this was applied on the skin by
means of a little stick. When the design was finished a thorn was
held in the left hand, while in the right hand was a small stick round
which strips of banana leaves were wound. The thorn was lightly
tapped with the stick until the pattern had been well punctured into
the skin.
PLATE XVI
A NATIVE OF BULAA
A BULAA YOUTH WITH RINGWORM
When a Papuan has a headache, or indeed any other kind of

ache, an attempt is generally made to alleviate the pain by letting
blood. Usually this is done by cutting the part affected with sharp
shells or fragments of glass, or with anything handy that has an
edge; but here, and in a few other places, the phlebotomy is also
performed by shooting with a diminutive bow and arrow. The bow is
made of two or three pieces of the mid-rib of palm leaflets tied
together, the string being a strand of vegetable fibre. The arrow is
also a mid-rib of a palm leaflet tipped with a splinter of glass
(originally a thorn formed the point); the shaft passes between two of
the components of the arc of the bow, and the butt is tied on to the
bow-string. Owing to this arrangement the arrow, when it is pulled
rhythmically and let go, punctures the skin on or about the same
spot.
Whilst in Bulaa I added very largely to my collection of samples of
the hair of the natives. The Papuan belongs to the group of men who
have dark skins and black woolly or frizzly hair. The hair is very
much like that of the true negro, but it grows much longer. In some
parts of New Guinea the hair is usually worn rolled into numerous
cords, which hang down all round the head like a thrum mop, but
among most of the people of the south-eastern part of the
Possession the hair is combed out so as to form a very characteristic
aureola, which is the glory of a Papuan dandy. It is astonishing,
however, the number of people one finds in this part of New Guinea
with curly, and even wavy hair. In a few cases the hair is almost quite
straight, whereas, as I have remarked, the hair of the typical Papuan
is frizzly or woolly, and so far as I am aware it is universally so
among the hill tribes of the interior, among the inhabitants of the
Papuan Gulf, and indeed all over the western portion of British New
Guinea. This variability in the character of the hair evidently points to
a racial mixture here. I was also surprised to find in this district the
tips of the hair vary from dark to quite a pale brown or a tan colour,
though the roots are black. I naturally put this down to bleaching,
owing to the use of lime for sanitary purposes; but Mr. English
assured me that it is a natural colour, a fact of some interest and
perplexity.
The marine pile dwellings of the village of Bulaa probably present,
at all events at a distance, much the same appearance as did the
lake dwellings of Central Europe in prehistoric times. People have
wondered how the primitive Swiss drove in the piles that supported
their houses. This question can only be answered approximately by
noting what people do nowadays. I therefore asked Mr. English to
arrange to have the process of pile-driving exhibited.
A post was procured, one end of which was roughly pointed, and
to the other extremity two long ropes were tied. One man scooped a
hole on the reef at low tide with his hands; the pile was then propped
up in the hole by several men. Two or three men steadied the post,
while several caught hold of each guy and gently swayed it to and
fro; the men who clasped the pole prevented it from overbalancing.
Gradually by its own weight the pile is thus wormed into the ground. I
was informed that when a pile is sunk actually in the sea a light
staging is erected near the top of the post; two or three men stand
on this framework, so that by their extra weight the pile may sink
more readily.
One day we saw Neolithic men making canoes at Keapara, and
here at Bulaa we saw the pile-dwellers at work with a marine pile-
village in the background.
I spent a fair amount of time on various occasions in getting a
number of small boys to make toys and play games, several of which
we photographed. Very little is known about the toys and games of
the children of savage peoples, and judging from the interest and
anthropological value of the study of the amusements of our own
children, these will prove an important field for research when more
facts are available. I played a good deal with the children, to their
and my amusement. I also showed them one or two of our games,
such as cock-fighting and hand-slapping; but I think they were not
sufficiently impressed by them to adopt them. I mention this,
however, in case a future traveller should find them still practised.
Toys made of leaves were common. The small boys cut off pieces
about ten to twelve inches in length from the origin of the leaves of a
tall, coarse grass that is used in thatching houses. The blade is split
off from each side of the mid-rib for about half its length; the two
flaps are twisted round the index finger of the right hand, and the
cleared mid-rib is held between the thumb and middle finger; the
hand is jerked, and the tearing off of the remaining portion of the
blade of the leaf gives a considerable impetus to the mid-rib, which
thus flies away like a miniature javelin. This was the simplest method
of playing, but there were three others, two of which necessitated the
use of both hands; the principle of gaining the impetus was the same
in all.
I was informed that this game is also played at Mawatta, a village
on the Torres Straits coast of British New Guinea, but I do not know
whether it occurs throughout the intermediate coast.
Rushes are twisted into diamond-shaped objects named kuru,
they are said to be stuck in houses for play. A Mawatta man claimed
that his people also made them, and said, “We look at hill, and make
him all the same.”
The following are all made of coconut palm leaves.
Lauga consists of two strips, each with three slits in them; the
puzzle is to make or to undo the interlacing as shown in the figure (p.
226).
The simple whirligig make is a very widely spread toy. It is also
found in the Solomon Islands in Melanesia, and in Funafuti (Ellice
Group) and Rotumah in Polynesia.
A toy wind instrument is made of strips of palm leaf wound spirally
so as to form a hollow cone or funnel, which varies from three inches
to about a foot in length. Inserted in the cavity are two long narrow
strips of leaf, or one long piece doubled upon itself; in either case
two similar ends project through the narrow orifice to form a “reed.”
It may not be amiss to explain that there are two main groups of
simple wind instruments that are blown by the mouth. In one the lips
are applied to the simple orifice, and it is their vibration intensified by
the sounding chamber of the instrument that produces the noise.
The conch shell and the trumpet are familiar examples of this group.
In the second group there is a vibrating arrangement which is
technically termed a “reed.” This group is divided into two classes:
(a) the “oboe” or “shawm” series in which the fixed or removable
mouthpiece is a tube, the ends of which are pinched together; (b) the
“clarinet” series which has a single vibrating tongue. The Bulaa toy
may be regarded as a kind of oboe.
I was delighted to find this musical toy, as I remembered that my
friend Henry Balfour, the curator of the Pitt-Rivers Museum at
Oxford, had recently written a paper on a very similar instrument, the
“whithorn,” which was made of spirally wound strips of willow bark. I
have since learned from Mr. Balfour that in Somersetshire these are
called “Mayhorns,” and very similar spirally twisted rude oboes (also
of bark) have been recorded from France, Germany, and Finland in
Europe. A spirally twisted palm-leaf trumpet(?) is found in West
Africa, and similar instruments from Flores, Sumatra, and Celebes,
but I am not quite certain of the exact nature of these latter. The
Bulaa name for this instrument is vili vili. A Mawatta man at Bulaa
told me his people made it, where it was called upa, but I was not
able to check this statement.
Fig. 26. Palm-leaf Toys, Bulaa
The occurrence of a reed instrument in this part of the world was

so surprising that further inquiries were necessary, and Mr. English
found out, after much questioning, that the toy was introduced by
Johnson, a West Indian negro.
Hereby hang two useful warnings, whether this fact be true or not.
First, not to assume an object is native to the district because it is
found there, but always to make inquiries. Secondly, the need for
investigations, for in a few years all knowledge of the origin of this
particular toy would be forgotten. These reflections hold good for
other objects in all parts of the world. A few months later I found that
at Mabuiag, in Torres Straits, a bent leaf of the karbe tree is used as
a whistle by blowing with it between the lips.
Once I thought I was on the track of a bull-roarer, and was much
excited thereby, as that remarkable implement has not been
recorded south-east of the Papuan Gulf; but kwari kwari proved to be
a new kind of toy that makes a noise like a fly buzzing, or the flying
of a large grasshopper. It is made of a strip of palm leaf bent upon
itself, one end of which is tied by a short bit of fine fibre to a long thin
mid-rib. The two flaps of the strip are kept apart by a thin bent mid-
rib of a palm leaflet. The whole is then whirled round.
A modification of the lauga puzzle is one in which the same strip of
palm leaf is cut into two links. On looking closely, one finds that it is
made thus: cut a piece of leaf (cardboard will do, but then the
method of manufacture is too evident) right through the thick lines in
the accompanying figure; cut half through the thickness of the leaf,
or card, along the dotted lines, then split the material between these
lines, and separate the upper and lower surfaces; the white portion
will come away from the shaded link, as in the second figure; the two
projecting spurs can be cut away if thought desirable. I cannot
imagine how the natives found this out—that is, if it is their own
invention; and they assure me such is the case.
Small cone shells are spun between the thumb and fingers like a
teetotum.
Our old friend leap-frog is also a diversion for Papuan boys, as it
occurs at such widely-spread places as Bulaa and Kiwai. A row of
boys stand in a line some distance apart on their hands and feet; the
last boy leaps over the others in succession, putting his hands on
their backs in the usual way. He then takes his place in front of the
others, and the now “last man” follows. This appears to be a very
widely-spread game. In Korea and Japan it is called “jumping over,”
and the same attitude on all-fours is taken there as in New Guinea.
In England we stand on our legs only, and “tuck in our tuppenny.”
We also saw the children indulging in the familiar pig-a-back
(pĕkĕkau), hopping (kaikai), jumping (puri), and skipping.
In the game called evanena two rows of boys face one another.
Each boy takes hold of the arm of the boy opposite him at or
immediately above or below the elbow with one hand, with the other
hand he clasps his own arm, right hand may grasp the left arm or
vice versâ. This position is similar to our “king’s chair” or “queen’s
chair” with the exception that we clasp the wrist and not the arm. As
all the boys stand close together they form a double row with a
platform of arms between them. A small boy is placed standing on
the arms of the last pair of boys, and he walks forward on those of
the boys in front. As soon as he has left the last pair of boys they
rush forward and place themselves in front of the others, and clasp
their arms as before. In this way a continuous platform is maintained,
and the game continues till the walker tumbles off. This game is also
played at Elevara, Port Moresby.
A variant which I saw played at Elevara is called omoro, or “frog.”
In this case the boy, instead of walking on the arms, lies full length
on his stomach, and is jerked up and down and at the same time
forwards. Ray also saw this game played at Saguana, Kiwai Island,
where it is called mere kereme beretsi (“boy-throwing”).
The prettiest revolving game was that known as maki gegelaki.
Four boys laid at full length on the ground at right angles to one
another, so as to form a cross, with their feet touching; usually they
placed a large piece of the husk of a coconut in the centre, against
which they tightly pressed their feet. A small boy crouched on their
feet to steady them. Four other boys stood between those lying
down; they caught hold of their hands; this raised the arms and
bodies of the latter. The standing boys walked round and round (right
hand to centre), and the whole contrivance revolved like a four-
spoked wheel.
Rapurapu. Four boys sit on the ground and interlock their legs in
the form of a square in such a way that the instep of the right foot
hooks over the pit of the knee of the boy to the right. They then stand
up and hop round on the left foot, clapping their hands rhythmically
and singing:—
“Rapu rapu tabai manu

Roroiatĕ atĕ atĕ
Roroiatĕ bada raita
Eaiimo eai eaiimo.”
As in Europe, the children have singing games, some of which I

have observed are:—
Kwaito pinupinu. A number of boys form a circle, catching hold of
each other’s hands, facing inwards. Two run into the circle and under
the arms of two other boys; when all the others have run under, the
last two twist themselves under their own arms, and the circle is now
complete again, but all the boys face outwards. They then revolve
sideways as fast as they can, gradually accelerating their speed till
one boy tumbles down. They all sing during the evolution:—
“Maru gĕno o, ana kwaito o, pinupinu o, kwaito pinupinu o,—ai!”
Mota ĕrĕmpto. A number of boys stand in a circle, each boy

catching hold of his neighbour’s wrists. One boy stands in the centre
with arms folded over his chest. The encircling boys sing:
“Mota erempto erempto

Bariva derempto derempto
Mota tim
Bariba tim
Pekuluoa waiau—o.”
This sounds like a challenge, and immediately the rhyme is

finished, the central boy rushes at the joined hands of any two boys
and tries to burst through. The game is finished when he succeeds.
Korikini. Some half-dozen boys sit in a circle very close together;
each holds the first or index finger of his hands upwards, closing the
thumb and other fingers of one hand on the extended index of the
other, or on that of another boy; in this way a column of hands is
made, the uppermost having its free index finger pointing upwards.
One boy alone has his right hand disengaged; with the forefinger he
taps the uppermost index finger crosswise. The following is sung
during the operation:—
Korikini korikini, papa raurirauri marire

Stick up finger crossing one another
Agiana korikoana karigămuai.
I look take away finger under armpit.
The top hand is then removed and placed under the armpit of the
nearest boy. The tapping song is repeated for the next hand, which
is similarly placed under the armpit of the boy that happens to be
nearest. When all have their hands placed under the armpits, the
same boy as before gently scratches each hand in rotation while
singing:—
Pika pika kiaka pa

Gaule aule kiaka pa.
The first hand to be released is placed in the middle of the player’s

palm uppermost, and each succeeding hand is placed upon it in the
same manner; sometimes the two hands of a player are placed side
by side; the whole pile of hands is raised up and down. One boy with
a disengaged hand gently taps the uppermost of the pile of hands
three times, holding his index finger vertically downwards while he
sings:—
Toitoi tutumu; keanai nunapakau.

Three times tap ear hold him.
At the end of the refrain the tapped hand is removed, and the
nearest ear of the next player is held by it. When all the hands have
been released and every ear is held by a hand, the players swing
their bodies backwards and forwards, and pulling each other’s ears
with more or less vigour, all sing:—
Mekeri aria
Pull one another.
Kiko aria.
This continues until one of the players gives in.

The words for the ear-pulling may apparently be varied, as some
children once sung:—
Wapuri poto
Kaia poto
i i i.
Mr. Ray saw the korikini game played at Saguane, where it is

called kuke.
Kinimali. This is a very similar game to the foregoing. The players,
however, pinch up the skin of the back of each other’s hands, the
slightly flexed hands being placed one on the top of the other. The
whole column is swayed up and down to the following song:—
Kinimali lĕkwa lĕkwa

Pinch flesh let go
Malawa kĕta kĕta
(name of a yam) (name of a yam)
Ana olio malauli
Run a little boy
Polaia polai.
Yellow
When this is finished, the top hand is placed at the bottom of the
column, palm uppermost, with extended fingers. The song is
repeated until all the hands are placed the one on the top of the
other. The Toitoi phase then finishes the game.
There appears to be considerable variation in these songs; we
found it very difficult to write them down, and when we did, it was still
more difficult to get a satisfactory translation; indeed, as with us at
home, some words do not appear to have a meaning. This is also
the case with many of the men’s legendary songs, the meaning of
which is now completely forgotten.
During our stay at Bulaa, we had one or two opportunities of
seeing the young people amuse themselves by dancing on the sand
beach. All those young men who had drums held them in their left
hands and beat them with their extended right hands; one man
rhythmically tapped the inside of his lime gourd with its spatula. The
girls edged themselves between the men, linking their arms within
those of the men. The drum-beats were in triplets ( ).
There was very little movement in the dancing. The men flexed their
knees slightly, and the girls swayed their petticoats laterally; in some
figures they swayed them backwards and forwards.
There were numerous figures, or separate small dances, in the
Bulaa dances. In one that was often repeated the majority of the
dancers formed a shaped group, lads and lassies alternating; all
these remained in their places. Other dancers, men only, advanced
in couples, beating their drums and capering up the central space. In
some figures the dancing men zigzagged across the space in a
prancing manner as they proceeded up and down; in others they
formed two parallel rows, all facing one side of the hollow oblong,
and pranced sideways a few steps up and down the space. Then
they jumped right round, so as to face the opposite way, and
repeated the same process; then back again, and so on. In this
dance the girls swayed their petticoats backwards and forwards.

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British Library Cataloguing-in-Publication Data

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3.1 Introduction 105

4.1 Introduction 131

5.1 Introduction 169

5.2 Evidence that unique chemistry was possible with main-group

6.1 Introduction 223

7.1 Introduction 279

8.1 Introduction 343

9.1 Introduction 393

10.1 Introduction: creatures proficient in inorganic solid-state chemistry 433

Carlos Alonso-Moreno Departamento de Quı́mica Inorgánica, Orgánica y

Christopher B. Caputo Department of Chemistry, York University, Toronto,

José A. Castro-Osma Departamento de Quı́mica Inorgánica, Orgánica y

Simon Duttwyler Department of Chemistry, Zhejiang University, Hangzhou,

M. Helena Garcia Centro de Quı́mica Estrutural and Departamento de

Mustapha Hamdaoui Department of Chemistry, Zhejiang University,

Helena Henke Institute of Polymer Chemistry, Johannes Kepler University,

Okan Icten Hacettepe University, Ankara, Turkey

Aitziber Iturmendi Institute of Polymer Chemistry, Johannes Kepler

Anukul Jana Tata Institute of Fundamental Research Hyderabad, Hyderabad,

Katie J. Lamb Green Chemistry Centre of Excellence, Department of

Agustı́n Lara-Sánchez Departamento de Quı́mica Inorgánica, Orgánica y

Di Li Institute for Energy Research, Jiangsu University, Zhenjiang, P.R. China

Fan Liu Department of Chemistry, Zhejiang University, Hangzhou, P.R. China

Shengqian Ma Department of Chemistry, University of South Florida, Tampa,

Cristina P. Matos Centro de Ciências e Tecnologias Nucleares (C2TN),

Meera Mehta Department of Chemistry, The University of Manchester,

Tânia S. Morais Centro de Quı́mica Estrutural and Departamento de Quı́mica e

Michael North Green Chemistry Centre of Excellence, Department of

George S. Pappas Institute of Polymer Chemistry, Johannes Kepler University,

Jizeng Sun Department of Chemistry, Zhejiang University, Hangzhou,

Qi Sun Department of Chemistry, University of South Florida, Tampa, FL,

Ian Teasdale Institute of Polymer Chemistry, Johannes Kepler University,

Ricardo G. Teixeira Centro de Quı́mica Estrutural and Departamento de

Ana Isabel Tomaz Centro de Quı́mica Estrutural and Departamento de

Andreia Valente Centro de Quı́mica Estrutural and Departamento de Quı́mica

Rajesh Varkhedkar Department of Chemistry, Zhejiang University,

Stephan E. Wolf Department of Materials Science and Engineering, Institute

Xiao Wu Green Chemistry Centre of Excellence, Department of Chemistry,

I was delighted to be asked to write this Foreword to Synthetic

While august multivolume collections such as the Comprehensive

on aluminum and iron for a variety of bond-forming and polymerization

chapters, however, take radically different approaches to this crucially

The use of metal complexes as catalysts in organic synthesis and polymer

Synthetic Inorganic Chemistry

complexes as industrial catalysts for the production of organic molecules or

1.2 Aluminum-based catalysts

Aluminum compounds have been used as catalysts for a broad range of

1.2.1 Reaction of three-membered ring heterocycles with

SCHEME 1.1 General mechanism for cyclic carbonate synthesis.

1. Non-precious metals in catalysis

at 110 C for 2 h in toluene, a series of functionalized and unfunctiona-