title: An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene.
abstract: The first N-donor-stabilized phosphasilene LSi(SiMe(3))═PSiMe(3) (L = PhC(NtBu)(2)) has been synthesized in 87% yield through 1,2-silyl migration of the (Me(3)Si)(2)P-substituted, N-heterocyclic silylene [LSi-P(SiMe(3))(2)]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph(3)PCl(2) to give the unprecedented 4π-electron Si(2)P(2)-cycloheterobutadiene [(LSi)(2)P(2)] with two-coordinate phosphorus atoms. The striking molecular structures as well as the (29)Si and (31)P NMR spectroscopic features of both products indicate the presence of zwitterionic Si═P bonds which is also in accordance with results by DFT calculations.
authors.affiliation: Institute of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17, Juni 135, Sekr. C2, D-10623 Berlin, Germany. shigeyoshi.inoue@mailbox.tu-berlin.de
authors.forename: Shigeyoshi
authors.initials: S
authors.lastname: Inoue
authors.forename: Wenyuan
authors.initials: W
authors.lastname: Wang
authors.forename: Carsten
authors.initials: C
authors.lastname: Präsang
authors.forename: Matthew
authors.initials: M
authors.lastname: Asay
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Irran
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess