The structures of [{RhLL′(μ-X)}2] [LL′ = cod, (CO)2, (CO)(PPh3) or {P(OPh)3}2; X = mt or taz], prepared from [{RhLL′(μ-Cl)}2] and HX in the presence of NEt3, 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.
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