title: Multiple bonding versus cage formation in organophosphorus compounds: the gas-phase structures of tricyclo-P3(CBu(t))2Cl and P≡C-Bu(t) determined by electron diffraction and computational methods.
abstract: The gas-phase structures of tricyclo-P(3)(CBu(t))(2)Cl and P≡C-Bu(t) have been determined by electron diffraction and associated quantum chemical calculations. Efforts to obtain detailed solid-state data for tricyclo-P(3)(CBu(t))(2)Cl have been thwarted by inability to prepare suitable crystalline material. Additional calculations for another tricyclic isomer of P(3)(CBu(t))(2)Cl and for two phosphorus-containing cyclopentadiene derivatives with pseudo-planar five-membered rings show that the experimentally observed isomer is more stable by at least 52 kJ mol(-1). Calculations for the equivalent structures with P atoms replaced by CH fragments have demonstrated that a ring structure is more favourable by over 200 kJ mol(-1) compared to each of two cage structures.
authors.affiliation: School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, UK EH9 3JJ.
authors.forename: Derek A
authors.initials: DA
authors.lastname: Wann
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Masters
authors.forename: Heather E
authors.initials: HE
authors.lastname: Robertson
authors.forename: Michael
authors.initials: M
authors.lastname: Green
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Kilby
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Russell
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones
authors.forename: David W H
authors.initials: DW
authors.lastname: Rankin