Inorganic Chemistry, Vol.50, No.6, 2064-2066, 2011
Mild P-4 Activation To Give an Anionic Diphosphorus Complex with a Dual Binding Ability at a Single P Site
The anion [Mo2Cp2(mu-PCy2)(mu-CO)(2)](-) (1; Li+ salt) reacts at 290 K with P-4 to give the diphosphorus-bridged complex [Mo2Cp2(mu-PCy2)(CO)(2)(mu-kappa(2): kappa(2)-P-2)](-) (2). The latter reacts with Mel and ClSnPh3 through a single P atom to give respectively diphosphenyl [Mo2Cp2(mu-PCy2)(CO)(2)(mu-kappa(2):kappa(2)-P2Me)] (3) and stannyl [Mo2Cp2(mu-PCy2)(CO)(2){mu-kappa(2):kappa(2)-P-2(SnPh3)}] (4) derivatives, with the P-P-Sn angle in 4 being unexpectedly acute [80.3(1)degrees]. According to density functional theory calculations, this novel nucleophilic behavior of is derived from its anionic nature, thus enabling the P-2 ligand to act in a pi-donor-like fashion.