A Contiguous Tricyclic [P6]2– Framework Spanning Across Two Vanadium(III) Centers

Abstract

The complex [(BDI)VCl(N{SiMe3}2)] (1) (BDI– = [ArNC(CH3)]2CH, Ar = 2,6-iPr2C6H3), a precursor readily prepared from metathesis of [(BDI)VCl2] and Na[N{SiMe3}2], can be reduced with Na/NaCl in the presence of white P4 to form a dinuclear species containing two VIII centers bridged by a tricyclic [P6]2– scaffold, namely, [(BDI)V(N{SiMe3}2)]2(μ-η1:η1-P6) (2). Coordination of [P6]2– involves a unique chairlike μ-η1:η1 binding mode with a contiguous tricyclic hexaphosphorus unit bridging across the two V centers. Complexes 1 and 2 have been structurally characterized, and a pathway toward the formation of the chairlike tricyclic [P6]2– scaffold in 2 is proposed.