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Covalency in Ce IV and U IV Halide and N‐Heterocyclic Carbene Bonds
Author(s) -
Arnold Polly L.,
Turner Zoë R.,
Kaltsoyannis Nikolas,
Pelekanaki Panagiota,
Bellabarba Ronan M.,
Tooze Robert P.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001471
Subject(s) - carbene , chemistry , halide , cerium , halogenation , molecule , medicinal chemistry , actinide , crystallography , inorganic chemistry , organic chemistry , catalysis
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‐ i Pr 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.