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