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

Robin J. Blagg, Maria J. Lopez-Gomez, Jonathan P. H. Charmant, Neil G. Connelly, John J. Cowell, Mairi F. Haddow, Alex Hamilton, A. Guy Orpen, Thomas Riis-Johannessen, Saowanit Saithong

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The structures of [{RhLL'(mu-X)}2] [LL' = cod, (CO)2, (CO)(PPh3) or {P(OPh)3}2; X = mt or taz], prepared from [{RhLL'(mu-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(mu-taz)}2], uniquely adopts a sulfur-eclipsed structure. The least hindered complex, [{Rh(CO)2(mu-mt)}2], shows intermolecular stacking of mt rings in the solid state. The complexes [{RhLL'(mu-X)}2] are chemically oxidised to trinuclear cations, [(RhLL')3(mu-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.
Original languageEnglish
Pages (from-to)11497-11510
Number of pages14
JournalDalton Transactions
Issue number43
Early online date27 Sep 2011
Publication statusPublished - 2011

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