title: Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane.
abstract: A proximate Lewis basic group facilitates the mild dehydrogenative P-As intramolecular coupling in the phosphine-arsine peri-substituted acenaphthene 3, affording thermally and hydrolytically stable arsanylidine-phosphorane 4 with a sterically accessible two-coordinate arsenic atom. The formation of 4 is thermoneutral due to the dehydrogenation being concerted with the donor coordination. Reaction of 4 with a limited amount of oxygen reveals arsinidene-like reactivity via formation of cyclooligoarsines, supporting the formulation of the bonding in 4 as base-stabilized arsinidene R3P→AsR.
authors.affiliation: EaStChem School of Chemistry, University of St. Andrews , Fife KY16 9ST, St. Andrews, U.K.
authors.forename: Brian A
authors.initials: BA
authors.lastname: Chalmers
authors.forename: Michael
authors.initials: M
authors.lastname: Bühl
authors.forename: Kasun S
authors.initials: KS
authors.lastname: Athukorala Arachchige
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.forename: Petr
authors.initials: P
authors.lastname: Kilian