ja502625z_si_005.cif (92.32 kB)
Geometrically Enforced Donor-Facilitated Dehydrocoupling Leading to an Isolable Arsanylidine-Phosphorane
dataset
posted on 2015-12-17, 01:54 authored by Brian
A. Chalmers, Michael Bühl, Kasun S. Athukorala Arachchige, Alexandra M. Z. Slawin, Petr KilianA 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.