bimetallic pd(iii) complexes in palladium-catalysed carbon ......aug 07, 2009 · bimetallic...
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Bimetallic Pd(III) Complexes in Palladium-Catalysed Carbon-Heteroatom Bond Formation
Wynter Gilson Literature Presentation
August 7, 2009
Powers, D. C.; Ritter, T. nature chem. 2009, 1, 302-309.
Palladium-Catalysed Carbon-Heteroatom Bond Formation
NPd(OAc)2
-AcOH
N
Pd
AcO
X2
Two-electronoxidation
Bimetallic reductive
elimination
N
X
2 Pd(II) + 2OAc + X + C13H8N
11
1
Pd(II)-d8- Pd(II)-d8
Square Planar
Pd(III)-d7- Pd(III)-d7
Octahedral
Pd(III)-Pd(III) Formation Followed by Bimetallic Reductive Elimination
PhICl2CH2Cl2, -30°C
Pd-Pd bondformation
23 °C, 2h
Bimetallic reduc.elimination
Pd(II) 4
96 %
3 94 %
N
1. AgOAc - AgCl2.
N
Cl +
Bond Distances: Pd(II) vs Pd(III)
Pd (III)
Pd (II)
Mechanistic Study
Mechanistic Study
Mechanistic Study
Mechanistic Study
Mechanistic Study
Bridging Acetate Ligand Replaced by Chealating Ligand
Deuterium Study
Palladium-Catalysed Reaction
Proposed Catalytic
Cycle