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ESSENTIALS OF
COORDINATION
CHEMISTRY
A Simplified Approach
with 3D Visuals
VASISHTA BHATT
UGC-Human Resource Development Centre
Sardar Patel University
Vallabh Vidyanagar, Gujarat, India
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 of others, including parties for whom they have a professional
responsibility.
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.
ISBN: 978-0-12-803895-6
xi
xii Preface
First of all, I must thank Elsevier Inc. for putting trust in my ability to
complete this work. I thank Cathleen Sether (Publishing Director), Katey
Birtcher (Senior Acquisitions Editor, Chemistry), Jill Cetel (Senior Editorial
Project Manager) and the entire Elsevier team for making this dream
journey a reality.
I sincerely acknowledge the support of the University Grants Com-
mission (UGC), New Delhi, India, for giving me an office and a position
from which I could comfortably complete this book; it would have been
impossible otherwise. The Vice Chancellor of Sardar Patel University,
Dr Harish Padh, has remained a prime source of my inspiration, as he is a
role-model scientist anyone would want to emulate. Dr A.R. Jani, the
Director of UGC-Human Resource Development Centre at Sardar Patel
University, was very happy when I took this assignment, and he readily
arranged for all the facilities that would make me comfortable in preparing
this book. He also provided vital scientific guidance. My fellow colleague,
Mr Vimal Shah, needs to be acknowledged for his valuable suggestions; as a
layman, it really helped me in predicting the learner’s perspective on
technical issues. The entire staff of my institute whole heartedly supported
me in this endeavour. Prof. Mangala Sunder Krishnan, IITM Chennai and
National Coordinator of the NPTEL, has remained the torch bearer in this
entire journey. The faculty members of the chemistry department of Sardar
Patel University, namely Prof. M.N. Patel, Prof. N.V. Sastry and Prof. D.K.
Raval, strongly encouraged me and offered all the guidance that I desired.
How can I forget the assistance provided by Mr Ravish Patel, who worked
as my assistant and helped me on each and every step!
My family remained the main driving force behind this project. I could
never have completed this book if they were not there. Sonal (my wife) and
Ishan (my son) contributed in all possible manners, beginning with the
sacrifice of their vacation outings. Both of them gave creative criticism and
suggestions on many pedagogical issues whenever I was in doubt. Mothers
and fathers are the first teachers of a child; Ramaben and Dineshbhai will be
the happiest people on the earth when this book takes its final form.
All the teachers and learners of coordination chemistry have knowingly
or unknowingly contributed a lot to this work. This book is now to be
tested for their expectations.
Vasishta Bhatt
xiii
CHAPTER 1
1. INTRODUCTION
The coordination compounds found their applications long before the
establishment of coordination chemistry. Bright red coloured alizarin dyes
were under applications even before the fifteenth century. This bright red
dye, now characterized as a chelated complex of hydroxyanthraquinone
with calcium and aluminium metal ions, is shown in Figure 1.
Later, in the sixteenth century, the formation of a well-known member
of today’s coordination chemistry family, the tetraamminecupric ion
in one of these orbitals while the other three remains half filled, an op-
portunity for three hydrogen atoms to contribute one electron each for the
formation of a covalent bond with nitrogen, can also be explained. Thus an
ammonia molecule has three NeH covalent bonds and one lone pair of
electrons over the nitrogen atom. It is worth noticing here that all the
valencies of all the atoms in both the molecules are fully satisfied and hence
there is no further scope of bonding.
A ‘complex’ situation arises when one comes to know that the molecule
CoCl3 can encompass six ammonia molecules, resulting into a third in-
dependent entity. This situation was fully understood and explained by
Werner’s coordination theory, followed by naming the entity as ‘complex’.
1.1 Definitions
Coordination compounds are the compounds containing one or more
coordinate covalent bonds.
Coordinate covalent bonds are the covalent bonds in which both the
bonding electrons are contributed by one of the bond partners. Figure 2
distinguishes the covalent bonds from the coordinate covalent bond in
NH3BF3. While the three BeF covalent bonds are formed due to the
sharing of electron pairs resulting from contributions of both boron and
fluorine atoms, an NeB bond is formed due to the donation of a lone pair
of electrons from nitrogen into the empty orbitals of boron. The coordinate
covalent bond is shown by an arrow with its head pointing towards the
direction of the donation of an electron pair, as shown in Figure 2.
A complex is a molecule/ion containing a central metal atom/ion
surrounded by a definite number of ligands held by secondary valences or
coordinate covalent bonds.
Primary valency refers to the charge over the metal ion e.g. Co(III)
has þ3 charge, which can be balanced by 3 charge-forming compounds
like CoCl3. The primary valency is ionic and is satisfied in the second
coordination sphere, as shown in Figure 3.
Secondary valency is the number of empty valence orbitals, as illus-
trated for [Co(NH3)6]Cl3 in the figure. The Co(III) ion has six empty
valence orbitals. Hence its secondary valency is six. Secondary valency is a
coordinate covalent valency, and it is satisfied in the first coordination
sphere of the metal ion, as shown in Figure 4.
Coordination number is a property of the metal ion representing the
total number of donor atoms directly attached to the central atom. In the
above case, the coordination number of Co(III) is six, as six nitrogen donor
atoms are directly connected to the central metal ion (cobalt(III)).
Ligand is any atom, ion or neutral molecule capable of donating an
electron pair and bonded to the central metal ion or atom through sec-
ondary valency.
H
H
H H
N H
C C C H Diethelenetrimine (dien), neutral, terdentate
N H
H C
H H H
H N
H
H C
O C O
O C N
C C Ethylenediaminetetraaceticacid (edta),
N C H
C C O anionic, sexadentate
H O O
C C H
O
Figure 5 Cont'd
8 Essentials of Coordination Chemistry
EXAMPLE CHARACTERISTICS
Oxalic acid
Anionic
Bidentate
Two covalent bonds
Two five-membered rings in the chelate
Glycine
Anionic
Bidentate
One covalent and one coordinate
covalent bond
Two five-membered rings in the chelate
1,10-phenanthroline
Neutral
Bidentate
Two coordinate covalent bonds
Two five-membered rings in the chelate
1,2,3-triaminopropane
Neutral
Tridentate
Three coordinate covalent bonds
Four five-membered rings and two
six-membered rings in the chelate
2,3-diaminopropanoicacid
Anionic
Tridentate
One covalent and two coordinate
covalent bonds
Four five-membered rings and two
six-membered rings in the chelate
Figure 6 Cont'd
2. NOMENCLATURE
A systematic nomenclature of coordination compounds requires a careful
consideration of the following rules [2]. The learner should first learn all of
these rules by heart and then do sufficient practice to master the procedure.
Figure 7 trans-[CoIIICl2(sal)(en)].
3. The anionic ligands are cited first and in alphabetical order, according to
the first symbols of their formulae.
4. The neutral and cationic ligands are then listed in the following order:
H2O, NH3, other inorganic ligands and organic ligands in alphabetical
order.
5. The structural information may be given by prefixes such as cis-, trans-,
fac-, mer- etc.
To illustrate the above rules, consider the writing of a coordination
formula for the compound shown in Figure 7 as trans-[CoIIICl2(sal)(en)].
N.B.: The ligand abbreviations and the formulae of the polyatomic
ligands are generally placed in parentheses.
Table 1 Names used for anionic ligands according to International Union of Pure
and Applied Chemistry (IUPAC) nomenclature
Ligand Name Ligand Name Ligand Name
F Fluoro OH Hydroxo O2 2 Peroxo
Cl Chloro CN Cyano CH3O Methoxo
Br Bromo HS Thiolo C5 H5 Cyclopentadienyl
I Iodo S2 Thio C6 H5 Phenyl
H Hydrido O2 Superoxo O2 Oxo
12 Essentials of Coordination Chemistry
Formula Name
4
[Fe(CN)6] Hexacyanoferrate(II) ion
[CoCl3(NH3)4] Triamminetrichlorocobalt(III)
[CuCl2(CH3NH2)2] Dichlorobis(methylamine)copper(II)
Cis-[PtCl2(NH3)2] Cis-diamminedichloroplatinum(II)
[PtCl(en)NH2NH3]þ2 Chloroethylenediaminehydraziniumplatinum(II)
ion
[Fe(CN)(CNCH2C6H5)5]þ Pentakis(benzylisocynide)cyano iron(III) ion
[Al(OH)(H2O)5]þ2 Pentaaquohydroxoaluminum(III) ion
[Co(CN)(CO)2NO] Dicarbonylcyanonitrosylcobaltate(0) ion
[PtClNO3(NH3)2(en)]SO4 Diammine(ethylenediamine)
chloronitroplatinum(IV) sulphate
K[SbCl5(C6H5)] Potassium pentachloro(phenyl) antimonite(V)
H2[PtCl6] Hexachloroplatinic(IV) acid
Na2[Fe(CN)5NO] Sodium pentacyanonitrosylferrate(III)
[PtPy4][PtCl4] Tetrakis(pyridine)platinum(II)
tetrachloroplatinate(II)
[Pt(NH3)4Br2]Br2 Tetramminedibromoplatinum(IV) bromide