Metal-Ligand Multiple Bonding in Thorium Phosphorus and Thorium Arsenic Complexes.

The complexes (C5 Me5 )2 Th(EHTipp)2 , (E=P or As; Tipp=2,4,6-triisopropylphenyl), provide a ligand framework that results in facile access to rare Th-E multiple bonds. The reaction of (C5 Me5 )2 Th(EHTipp)2 with KN(SiMe3 )2 , proceeds cleanly to the desired bridging phosphinidiide or arsinidiide complex, [{(C5 Me5 )2 Th(μ2 -ETipp)(μ2 -EHTipp)}K]2 under ambient conditions. In the absence of a chelating agent, the potassium cation of one monomeric unit interacts with the aryl ring of a second monomer to form a bridged dimer. In the presence of 2,2,2-cryptand, the terminal phosphinidene complex, [(C5 Me5 )2 Th=PTipp(PHTipp)][K(2,2,2-cryptand)] is isolated. Using X-ray crystallographic analysis, we have determined these complexes display the shortest Th-P and Th-As bond lengths reported.