title: Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBu(t))2: a novel route to polyphosphorus phosphenium complexes.
abstract: Substitution of Cl(-) in the tricyclic triphosphorus cage Cl(P(1))-P3(CBu(t))2 by a range of both anionic and neutral nucleophiles has been investigated. With anionic nucleophiles, reaction with fluoride and hydride anion was shown to afford F(P(1))-P3(CBu(t)) and H(P(1))-P3(CBu(t))2 respectively. Subsequent deprotonation of the latter results in the formation of the aromatic anion [1,2,4-P3(CBu(t))2]-. With neutral nucleophiles, addition of either PMe3 or PEt3 to Cl(P(1))-P3(CBu(t))2 in the presence of TlOTf results in the formation of the phosphine-phosphenium complexes [(R3P(P(1))-P3(CBu(t))2][OTf] (R = Me or Et): the structure of the methyl-substituted compound was determined by a single crystal X-ray diffraction study. The phosphine ligand in these complexes is extremely labile and addition of I2 to [(Me3P(P(1))-P3(CBu(t))2]+ results in the formation of I(P(1))-P3(CBu(t))2.
authors.affiliation: Department of Chemistry, University of York, Heslington, York, UK.
authors.forename: Charlotte E
authors.initials: CE
authors.lastname: Willans
authors.forename: Cheryl
authors.initials: C
authors.lastname: Fish
authors.forename: Michael
authors.initials: M
authors.lastname: Green
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Kilby
authors.forename: Jason M
authors.initials: JM
authors.lastname: Lynam
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Russell
authors.forename: Adrian C
authors.initials: AC
authors.lastname: Whitwood