dc.contributor.author | Nieuwenhuyzen, Mark | |
dc.contributor.author | Saunders, Graham C. | |
dc.contributor.author | Smyth, E.C.M. Sarah | |
dc.date.accessioned | 2009-03-30T21:27:48Z | |
dc.date.available | 2009-03-30T21:27:48Z | |
dc.date.issued | 2006 | |
dc.identifier.citation | Nieuwenhuyzen, 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.uri | https://hdl.handle.net/10289/2073 | |
dc.description.abstract | The 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.iso | en | |
dc.publisher | American Chemical Society | en |
dc.relation.uri | http://pubs.acs.org/doi/abs/10.1021/om050893%2B | en |
dc.subject | chemistry | en |
dc.title | 1,2-Bis{(pentafluorophenyl)phenylphosphino}ethane: A Probe for Configurational Stability in Three-Legged Piano Stool Complexes | en |
dc.type | Journal Article | en |
dc.identifier.doi | 10.1021/om050893+ | en |
dc.relation.isPartOf | Organometallics | en_NZ |
pubs.begin-page | 996 | en_NZ |
pubs.elements-id | 33737 | |
pubs.end-page | 1003 | en_NZ |
pubs.issue | 4 | en_NZ |
pubs.volume | 25 | en_NZ |