The oxidative conversion of the N,S-bridged complexes [{RhLL'(µ-X)}2] to [(RhLL')3)(µ-X)2]+ (X = mt or taz): a comparison with the oxidation of N,N-bridged analogues.

The structures of [{RhLL'(µ-X)}(2)] [LL' = cod, (CO)(2), (CO)(PPh(3)) or {P(OPh)(3)}(2); X = mt or taz], prepared from [{RhLL'(µ-Cl)}(2)] and HX in the presence of NEt(3), depend on the auxiliary ligands LL'. The head-to-tail arrangement of the two N,S-bridges is accompanied by a rhodium-eclipsed conformation for the majority but the most hindered complex, [{Rh[P(OPh)(3)](2)(µ-taz)}(2)], uniquely adopts a sulfur-eclipsed structure. The least hindered complex, [{Rh(CO)(2)(µ-mt)}(2)], shows intermolecular stacking of mt rings in the solid state. The complexes [{RhLL'(µ-X)}(2)] are chemically oxidised to trinuclear cations, [(RhLL')(3)(µ-X)(2)](+), most probably via reaction of one molecule of the dimer, in the sulfur-eclipsed form, with the fragment [RhLL'](+) formed by oxidative cleavage of a second.