Migratory insertion of benzonitrile into both An−C bonds of the bis(alkyl) and bis(aryl) complexes (C5Me5)2AnR2 yields the actinide ketimido complexes (C5Me5)2An[−NC(Ph)(R)]2 (where An = Th, R = Ph, CH2Ph, CH3; An = U, R = CH2Ph, CH3) and provides a versatile method for the construction of electronically and sterically diverse ketimide ligands. The Th(IV) compounds represent the first examples of thorium ketimide complexes. The uranium complexes are surprisingly unreactive, and both the uranium and thorium bis(ketimido) complexes display unusual electronic structure properties. The combined chemical and physical properties of these complexes suggest a higher An−N bond order due to significant ligand-to-metal π-bonding in the actinide ketimido interactions and indicate that the f-electrons in mid-valent organouranium complexes might be far more involved in chemical bonding and reactivity than previously thought. We also report herein the structures of the known thorium and uranium complexes (C5Me5)2Th(CH2Ph)2, (C5Me5)2ThMe2, (C5Me5)2U(CH2Ph)2, and (C5Me5)2UMe2.

The air-stable complex Cp(PMe(3))IrCl(2) efficiently catalyzes the exchange of deuterium from D(2)O into both activated and unactivated C-H bonds of organic molecules without added acid or stabilizers. Selectivity is observed in many cases, with activation of primary C-H bonds occurring preferentially. A number of new stoichiometric transformations involving the iridiym catalyst precursor are also presented, including an oxidation-decarbonylation reaction with primary alcohols.

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