%0 Generic %A Chalmers, Brian A. %A Bühl, Michael %A S. Athukorala Arachchige, Kasun %A M. Z. Slawin, Alexandra %A Kilian, Petr %D 2015 %T Geometrically Enforced Donor-Facilitated Dehydrocoupling Leading to an Isolable Arsanylidine-Phosphorane %U https://acs.figshare.com/articles/dataset/Geometrically_Enforced_Donor_Facilitated_Dehydrocoupling_Leading_to_an_Isolable_Arsanylidine_Phosphorane/2032428 %R 10.1021/ja502625z.s005 %2 https://acs.figshare.com/ndownloader/files/3603738 %K dehydrogenative %K sterically %K 3P %K intramolecular %K Isolable %K formulation %K acenaphthene %K arsenic %K reactivity %K thermoneutral %K donor coordination %K formation %K dehydrogenation %K cyclooligoarsine %K Enforced %K Lewis %K arsinidene %K Dehydrocoupling %K Geometrically %K hydrolytically %X 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. %I ACS Publications