The oxidative conversion of the N,S-bridged complexes [{RhLL '(mu-X)}(2)] to [(RhLL ')(3)(mu-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

Research output: Contribution to journalArticle (Academic Journal)peer-review

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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
Publication statusPublished - 2011

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