Bi-P Bond Homolysis as a Route to Reduced Bismuth Compounds and Reversible Activation of P4.

Bismuth diphenylphosphanides Bi(NONR )(PPh2 ) (NONR =[O(SiMe2 NR)2 ], R=tBu, 2,6-iPr2 C6 H3 , Aryl) undergo facile decomposition via single-electron processes to form reduced Bi and P species. The corresponding derivatives Bi(NONR )(PCy2 ) are stable. Reaction of the isolated BiII radical . Bi(NONAr ) with white phosphorus (P4 ) proceeds with the reversible and selective activation of a single P-P bond to afford the bimetallic μ,η1:1 -bicyclo[1.1.0]tetraphosphabutane compound.