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dc.contributor.authorNieuwenhuyzen, Mark
dc.contributor.authorSaunders, Graham C.
dc.contributor.authorSmyth, E.C.M. Sarah
dc.date.accessioned2009-03-30T21:27:48Z
dc.date.available2009-03-30T21:27:48Z
dc.date.issued2006
dc.identifier.citationNieuwenhuyzen, M., Saunders, G.C. & Smyth, E.C.M.S. (2006). 1,2-Bis{(pentafluorophenyl)phenylphosphino}ethane: A Probe for Configurational Stability in Three-Legged Piano Stool Complexes. Organometallics, 25(4), 996-1003.en
dc.identifier.urihttp://hdl.handle.net/10289/2073
dc.description.abstractThe pentafluorophenyl-substituted diphosphine (C₆F₅)PhPCH₂CH₂PPh(C₆F₅) has been prepared, as a 1:1.7 mixture of rac (1a) and meso (1b) isomers, in four steps from dppe. The reaction between [Cp*RhCl(μ-Cl)]2 and 1 in the presence of tetrafluoroborate yielded a mixture of racemic diastereoisomers of [Cp*RhCl(κP,κP-1a)][BF₄] (4a•BF₄) and trans and cis isomers of [Cp*RhCl(κP,κP-1b)][BF₄] (4b•BF₄ and 4c•BF₄, respectively). On addition of Proton Sponge, 4a and 4c, in which at least one pentafluorophenyl group is close to the pentamethylcyclopentadienyl ligand, underwent rapid dehydrofluorinative carbon−carbon coupling giving trans- and cis-[{η⁵,κP,κP-C₅Me₄CH₂C₆F₄-2-PPhCH₂CH₂PPh(C₆F₅)}RhCl]⁺ (5 and 6), respectively. The latter underwent further dehydrofluorinative carbon−carbon coupling to give two isomers of [{η⁵,κP,κP-C₅Me₃[CH₂C₆F₄-2-PPhCH₂]₂}RhCl]+ (7). Isomerization of 4b to 4c was observed in chloroform and dimethlysulfoxide. Neither isomerization of 4a to 4b or 4c nor isomerization of 5 to 6 was observed at ambient or elevated temperature in dimethyl sulfoxide. The results provide the first evidence that complexes of η⁵,κP,κL-cyclopentadienyl-phosphine-donor ligands are configurationally stable at high temperature.en
dc.language.isoen
dc.publisherAmerican Chemical Societyen
dc.relation.urihttp://pubs.acs.org/doi/abs/10.1021/om050893%2Ben
dc.subjectchemistryen
dc.title1,2-Bis{(pentafluorophenyl)phenylphosphino}ethane: A Probe for Configurational Stability in Three-Legged Piano Stool Complexesen
dc.typeJournal Articleen
dc.identifier.doi10.1021/om050893+en
dc.relation.isPartOfOrganometallicsen_NZ
pubs.begin-page996en_NZ
pubs.elements-id33737
pubs.end-page1003en_NZ
pubs.issue4en_NZ
pubs.volume25en_NZ


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