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Covalency in Ce-IV and U-IV Halide and N-Heterocyclic Carbene Bonds

Arnold, PL; Turner, ZR; Kaltsoyannis, N; Pelekanaki, P; Bellabarba, RM; Tooze, RP; (2010) Covalency in Ce-IV and U-IV Halide and N-Heterocyclic Carbene Bonds. CHEM-EUR J , 16 (31) 9623 - 9629. 10.1002/chem.201001471.

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Abstract

Oxidative halogenation with trityl chloride provides convenient access to Ce-IV and U-IV chloroamides [M(N{SiMe3}(2))(3)Cl] and their N-heterocyclic carbene derivatives, [M(L)(N-{SiMe3}(2))(2)Cl] (L= OCMe2CH2(CNCH2-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{SiMe3}(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.

Type:Article
Title:Covalency in Ce-IV and U-IV Halide and N-Heterocyclic Carbene Bonds
DOI:10.1002/chem.201001471
Keywords:actinides, computational chemistry, covalency, lanthanides, N-heterocyclic carbenes, DENSITY-FUNCTIONAL THEORY, LANTHANIDE(III)/ACTINIDE(III) DIFFERENTIATION, TETRAPYRROLE LIGANDS, CERIUM(IV) COMPLEXES, ELECTRONIC-STRUCTURE, SANDWICH COMPLEXES, PORPHYRIN LIGANDS, CRYSTAL-STRUCTURE, OXIDATION-STATE, METAL-COMPLEXES
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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