The Stepwise Reaction of Rhodium and Iridium Complexes of Formula [MCl (κ C,N,N',P-L)] with Silver Cations: A Case of trans-Influence and Chiral Self-Recognition.

Acetonitrile suspensions of the dichlorido complexes [MCl (κ C,N,N',P-L)] [M=Rh (1), Ir (2)] react with AgSbF in a 1:2 molar ratio affording the bis-acetonitrile complexes [M(κ C,N,N',P-L)(NCMe) ][SbF ] (3 and 4). The reaction takes place in a sequential manner and the intermediates can be isolated varying the M:Ag molar ratio. In a 2:1 molar ratio, it affords the dimetallic monochlorido-bridged compounds [{MCl(κ C,N,N',P-L)} (μ-Cl)][SbF ] (5 and 6).