Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane
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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.
Chalmers , B A , Buehl , M , Athukorala Arachchige , K S , Slawin , A M Z & Kilian , P 2014 , ' Geometrically enforced donor-facilitated dehydrocoupling leading to an isolable arsanylidine-phosphorane ' Journal of the American Chemical Society , vol 136 , no. 17 , pp. 6247-6250 . DOI: 10.1021/ja502625z
Journal of the American Chemical Society
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