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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 40; no. 43; pp. 11497 - 11510
• Main Authors: Blagg, Robin J, López-Gómez, María J, Charmant, Jonathan P H, Connelly, Neil G, Cowell, John J, Haddow, Mairi F, Hamilton, Alex, Orpen, A Guy, Riis-Johannessen, Thomas, Saithong, Saowanit
• Format: Journal Article
• Language: English
• Published: England 01.01.2011
• Subjects: Cations; Cleavage; Conversion; Dimers; Fragmentation; Ligands; Solid state; Stacking
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c1dt10930h

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.