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). In a 1:1 molar ratio, the monosubstituted solvato-complexes [MCl(κ C,N,N',P-L)(Solv)][SbF ] (Solv=H O, MeCN, 7-10) were obtained. Finally, in a 2:3 molar ratio, it gives complexes 11 and 12 of formula [{M(κ C,N,N',P-L)(NCMe)(μ-Cl)} Ag][SbF ] in which a silver cation joints two cationic monosubstituted acetonitrile-complexes [MCl(κ C,N,N',P-L)(NCMe)] through the remaining chlorido ligands and two Ag⋅⋅⋅C interactions with one of the phenyl rings of each PPh group. In all the complexes, the aminic nitrogen and the central metal atom are stereogenic centers. In the trimetallic complexes 11 and 12, the silver atom is also a stereogenic center. The formation of the cation of the dimetallic complexes 5 and 6, as well as that of the trimetallic complexes 11 and 12, takes place with chiral molecular self-recognition. Experimental data and DFT calculations provide plausible explanations for the observed molecular recognition. The new complexes have been characterized by analytical, spectroscopic means and by X-ray diffraction methods.