Formation of a Bridging Phosphinidene Thorium Complex.

The synthesis and structural determination of the first thorium phosphinidene complex are reported. The reaction of 2 equiv of (C5Me5)2Th(CH3)2 with H2P(2,4,6-(i)Pr3C6H2) at 95 °C produces [(C5Me5)2Th]2(μ2-P[(2,6-CH2CHCH3)2-4-(i)PrC6H2] as well as 4 equiv of methane, 2 equiv from deprotonation of the phosphine and 2 equiv from C-H bond activation of one methyl group of each of the isopropyl groups at the 2- and 6-positions. Transition state calculations indicate that the steps in the mechanism are P-H, C-H, C-H, and then P-H bond activation to form the phosphinidene.