Structural, Spectroscopic, and Computational Analysis of Heterometallic Thorium Phosphinidiide Complexes

To synthesize complexes with thorium-phosphorus multiple-bond character, reactions of (C5Me5)(2)Th[P(H)Mes](2) with monovalent alkali-metal bases, MN(SiMe3)(2), as well as CuMes, have been investigated. The results with MN(SiMe3)(2) are phosphinidiide complexes of the form {(C5Me5)(2)Th[mu(2)-P(Mes)][mu(2)-P(H)Mes]M(L)(n)}(2) (M = Na, n = 0; M = K, L = THF, n = 1; M = Rb, L = THF, n = 1; M = Cs, L = Et2O, n = 1). With CuMes, the product is a Th2Cu3P5 heterometallic structure, {(C5Me5)(2)Th[(mu(2)-P(H)Mes)P(Mes)]Cu}(2)Cu[mu(2)-P(H)Mes]. All complexes have been characterized using heteronuclear NMR and IR spectroscopy, density functional theory calculations, and their solid-state structure identified by X-ray crystallography. We also report the structure of {(C5Me5)(2)Th[(mu(2)-As(H)Mes)As(Mes)]Cu}(2)Cu[mu As-2(H)Mes] obtained from (C5Me5)(2)Th[As(H)Mes](2) with CuMes.