Inorganic Chemistry, Vol.33, No.12, 2501-2502, 1994
A Tetranuclear Rhodium Complex with a Mu-4-S Ligand, ((CP-Asterisk-2Rh2(Mu-2-CH2)2)2(Mu-4-S))2+ (CP-Asterisk = Eta-5-C5Me5), Obtained from Stepwise Abstraction of the SH- Ligand from a Dinuclear Rhodium Dihydrosulfide Precursor by Ag+
A strong oxidant-Ag+ in CH2Cl2-instead of oxidation, induces an intriguing partial abstraction of the terminal SH- ligand in trans-[Cp*2Rh2(mu2-CH22(SH)2] to give [Cp*2Rh2(mu2-CH2)2(mu2-SH)]+ followed by abstraction of the bridging SH- ligand in [Cp*2Rh2(mu2-CH2)2(mu2-SH)]+ to form a tetranuclear mu4-S cationic complex [{Cp*2Rh2(mu2-CH2)2}2-(mu4-S)]2+. Further abstraction of the mu4-ligand of [{Cp*2Rh2(mu2-CH2)2}2(mu4-S)]2+ by Ag+ takes place slowly with formation of a completely S atom-abstracted product [Cp*2Rh2(mu2-CH2)2(mu2-O2CMe)]+. The mu4-S ligand in [{Cp*2Rh2(mu2-CH2)2}2(mu4-S)]2+ has tetrahedral geometry and a spiran type linkage with two metal-metal-bonded dinuclear units. This is the first example of a mu3-S spiran sulfide complex of rhodium.
Keywords:CRYSTAL-STRUCTURE;SULFIDO LIGANDS;CLUSTER COMPOUNDS;METAL COMPLEXES;SULFUR;HYDROGEN;MU-S(W(CO)5)22;W(CO)5(SH);REDUCTION;MECHANISM