Covalency in Ce(IV) and U(IV) halide and N-heterocyclic carbene bonds

Chemistry : a European Journal
Polly L ArnoldRobert P Tooze

Abstract

Oxidative halogenation with trityl chloride provides convenient access to Ce(IV) and U(IV) chloroamides [M(N{SiMe(3)}(2))(3)Cl] and their N-heterocyclic carbene derivatives, [M(L)(N{SiMe(3)}(2))(2)Cl] (L = OCMe(2)CH(2)(CNCH(2)CH(2)NDipp) Dipp = 2,6-iPr(2)C(6)H(3)). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe(3)}(2))(2)F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

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Citations

Dec 23, 2015·Inorganic Chemistry·Jee Eon KimEric J Schelter
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Dec 10, 2013·Inorganic Chemistry·Ursula J WilliamsEric J Schelter

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