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Geometrically Enforced Donor-Facilitated Dehydrocoupling Leading to an Isolable Arsanylidine-Phosphorane

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posted on 17.12.2015, 01:53 by Brian A. Chalmers, Michael Bühl, Kasun S. Athukorala Arachchige, Alexandra M. Z. Slawin, Petr Kilian
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.