The chemistry of phosphirane-substituted phosphinidene complexes

Abstract

Thermolysis of the 1,1′-biphosphirane pentacarbonylmetal complex offers access to 3,4-dihydro-1,2-diphosphete and diphosphorus (P₂) intermediates. A control reaction proves that this step-wise reaction is initiated by the dissociation of a W(CO)₅ group. DFT calculations predict that further transformations proceed via a transient phosphiranylphosphinidene complex. The formation of the 3,4-dihydro-1,2-diphosphete derivative is thermodynamically favored, while a kinetic process provides the diphosphorus (P₂) complex.