title: 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.
abstract: 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.
authors.affiliation: School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK.
authors.forename: Robin J
authors.initials: RJ
authors.lastname: Blagg
authors.forename: María J
authors.initials: MJ
authors.lastname: López-Gómez
authors.forename: Jonathan P H
authors.initials: JP
authors.lastname: Charmant
authors.forename: Neil G
authors.initials: NG
authors.lastname: Connelly
authors.forename: John J
authors.initials: JJ
authors.lastname: Cowell
authors.forename: Mairi F
authors.initials: MF
authors.lastname: Haddow
authors.forename: Alex
authors.initials: A
authors.lastname: Hamilton
authors.forename: A Guy
authors.initials: AG
authors.lastname: Orpen
authors.forename: Thomas
authors.initials: T
authors.lastname: Riis-Johannessen
authors.forename: Saowanit
authors.initials: S
authors.lastname: Saithong