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SE OMC Part1 2023
SE OMC Part1 2023
CATALYSIS
COURSE TOPICS
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NOBEL PRIZES IN
ORGANOMETALLIC CHEMISTRY
• 1912 Victor Grignard and Paul Sabatier for Grignard reagent and hydrogenation reactions
• 1963 Karl Ziegler and Giulio Natta on Ziegler-Natta catalyst, Olefin polymerization
• 2001 W. S. Knowles, Ryōji Noyori and Karl Barry Sharpless for asymmetric hydrogenation and oxidation
reactions
• 2005 Yves Chauvin, Robert Grubbs, and Richard Schrock on metal-catalyzed alkene metathesis
• 2010 Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for palladium catalyzed cross coupling reactions
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Well-Known Organometallic Homogeneous Catalysts Used in Industry
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Catalysis: A sustainable future
Catalyst
development
Circular Economy: Sustainable development
TOWARDS ZERO WASTE
[Ni-Fe] hydrogenase
H2 production and activation
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OUTLINE
References
• Organotransition metal chemistry: From bonding to catalysis by John F. Hartwig, University Science Books, 2010
• Organometallic chemistry and catalysis by Didier Astruc, Springer, 2007
• Applied Organometallic Chemistry and Catalysis by Robin Whyman, Oxford University Press, 2003
• Organometallic Chemistry by Gary O. Spessard and Gary L. Miessler, Prentice Hall, Inc., 1997
• The Organometallic Chemistry of the Transition Metals by Robert H. Crabtree, Wiley Interscience;
• Basic Organometallic Chemistry: Concepts, Syntheses and Applications by Gupta and Elias
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OXIDATION NUMBERS
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THE THREE FAMILIES OF LIGANDS L, X AND Z
L type ligands
X type ligands
• They give one single electron to the metal during the bond formation
• The valence number is modified of one unit
Z-type ligand
• The metal gives two paired electrons to the ligand during the bond formation
• Examples: BX3, AlX3, SO2…
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THE FUNDAMENTAL REACTIONS
IN ORGANOMETALLIC CHEMISTRY
Some fundamental reactions permit to explain in a rational way of the reactivity in organometallic chemistry.
4. b hydride elimination
5. Ligands Substitution
7. Coupling
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OXIDATIVE ADDITION
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Oxidative Addition
Oxidative addition (OA) via C-H bond activation
OA may occur intramolecularly. Intramolecular additions of this type are called cyclometallations or, more
specifically, an orthometallation in the case shown
This type of reactions help to activate unreactive hydrocarbons such as methane – known as C-H activation
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Classes of A-B Polar Non- Ligands
polar with pi
system
HX H2, X2 O2
(X=halog
en)
R-X R-H Alkene
Cis
Main pathways
Trans
1. Concerted
2. SN2
3. Radical
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3-Center Concerted Addition
Concerted, or three-centre, OA is an associative reaction in which the incoming ligand first binds as a σ complex and
then undergoes bond breaking
Addition of H2
π-acidic ligands love the equatorial sites of the TBP geometry, which are rich in electrons capable of π
bonding. As a consequence, π-acidic ligands get folded back preferentially and tend to end up cis to their trans
partners in the starting complex.
Dihydrogen may approach along two distinct trajectories. Placing π-acidic ligands in the equatorial plane of the
TBP transition state is favored.
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3-Center Concerted Addition
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3-Center Concerted Addition
Addition of C–H • Oxidative addition of Si-H and Sn-H also concerted
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Cyclometallations
Yale University
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Agostic (to hold on to oneself) interactions
• In the mid1960s it was observed that certain transition metal complexes exhibited close
proximity of C-H bonds of their coordinating ligands to the metal atoms.
Maurice S. Brookhart
University of Houston
• In 1983 Brookhart and Green coined the word agostic to describe such weak
bonding interaction between hydrogen atoms of aliphatic C-H and aromatic C-H
bonds with metal centre
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SN2 pathway
• These reactions proceed via a polar transition state that is accompanied by an inversion of the stereochemistry
at the atom of attack by the metal center.
• The SN2 mechanism is often found in the addition of methyl, allyl, acyl, and benzyl halides, as is the case for
Vaska’s complex.
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Ligands with pi system
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Radical Pathways
• Less desirable are oxidative additions involving radicals, because these reactive intermediates tend to give
undesired side-reactions
a) Non-chain radical mechanism
The nonchain variant applies to OA of alkyl halides, RX, to Pt(PPh3)3 (RX = MeI, EtI, or PhCH2Br).
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Oxidative Addition
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Oxidative coupling
• Two L type ligands, coordinated to the same metal center are coupled to lead to a metallacycle via the formation
of a bond between the two L type ligands.
• The oxidative coupling is the key step for the formation of carbon cycles and in olefin metathesis reactions.
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REDUCTIVE ELIMINATION
• The reductive elimination is the reverse fundamental reaction of the oxidative addition. In general, the two
X type ligands must be in a cis position in order to undergo reductive elimination and lead to a X-X
molecule.
Example:
It is often the last step in catalytic cycles
(hydrogenation, hydroformylation, cross-
coupling reactions…).
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Factors Favouring Reductive Elimination (RE)
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Reductive Elimination (RE)
• It’s been observed in a number of cases that a ligand dissociates from octahedral complexes to form a
distorted TBP geometry brings the eliminating groups closer to one another to facilitate elimination.
• Square planar complexes may either take on an additional fifth ligand or lose a ligand to form an odd-coordinate
complex before reductive elimination.
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Reductive Elimination (RE)
Large bite angles of diphosphines have been shown to enhance the rates of reductive elimination by bringing the
two departing ligands closer together. 34
LIGAND SUBSTITUTION
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Associative Substitution: Nature of the nucleophile
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Associative Substitution: Sterics
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Reference:
M.C. White/Q. Chen Chem
153
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Ring-slippage chemistry of transition metal cyclopentadienyl and indenyl
complexes; Chem. Rev. 1987, 87, 2, 307–318.
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Ligand dissociation: Heat or Light
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Ligand dissociation: Solvent effect
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Organometallic Reactions
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Insertion Reactions
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MIGRATORY INSERTION
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Migration Vs Insertion
We generally do NOT worry about the exact pathway, that is why we use the term “migratory insertion” to indicate
that either directional pathway is fine.
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ALKENE INSERTION
• The insertion of coordinated alkenes into M–H or M-R bonds leads to metal alkyls and constitutes a key
step in a variety of catalytic reactions including alkene polymerization, the most commercially important
reaction.
• Like 1,1-insertions, 1,2-insertions generate a vacant site on the metal, which is usually filled by an external
ligand.
The transition state for insertion has an essentially coplanar M−C−C−H arrangement, and this implies that both insertion
and elimination also require the M−C−C−H system to be capable of becoming coplanar.
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ALKENE INSERTION
Hydrozirconation
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b-Hydride Elimination
Beta-hydride elimination is a reaction in which an alkyl group having a b hydrogen, bonded to a metal centre is
converted into the corresponding metal-bonded hydride and a bonded alkene. The alkyl must have hydrogens on the
beta carbon. The metal complex must have an empty (or vacant) site cis to the alkyl group for this reaction to occur.
H H H H H
H H H
C H C C
M
M C M C C Can either be a vital step in a reaction or an unwanted
H H H H H H side reaction
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Transmetalation
The transfer of an organic group from one metal center to another. The process involves no formal change in
oxidation state for either metal.
Transmetalation reagents
• Favored when the metal fragment is a poor π base but a good σ acid.
• Complex bears a net positive charge or has electron-withdrawing
ligands
• reduce the hapticity hapticity of the ligands