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

Blagg, Robin J., Lopez-Gomez, Maria J., Charmant, Jonathan P. H., Connelly, Neil G., Cowell, John J., Haddow, Mairi F., Hamilton, Alex, Orpen, A. Guy, Riis-Johannessen, Thomas and Saithong, Saowanit (2011) 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. Dalton Transactions, 40 (43). pp. 11497-11510. ISSN 1477-9226

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Abstract

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.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Pure Connector
Date Deposited: 14 Mar 2014 12:32
Last Modified: 21 Apr 2020 22:56
URI: https://ueaeprints.uea.ac.uk/id/eprint/48128
DOI: 10.1039/c1dt10930h

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