Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds

被引：133

作者：

Arnold, Polly L. ^{[1
]}

Turner, Zoe R. ^{[1
]}

Kaltsoyannis, Nikolas ^{[2
]}

Pelekanaki, Panagiota ^{[2
]}

Bellabarba, Ronan M. ^{[3
]}

Tooze, Robert P. ^{[3
]}

机构：

[1] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland

[2] UCL, Dept Chem, London WC1H 0AJ, England

[3] Sasol Technol UK, St Andrews KY16 9SR, Fife, Scotland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 31期

基金：

英国工程与自然科学研究理事会;

关键词：

actinides; computational chemistry; covalency; lanthanides; N-heterocyclic carbenes; LANTHANIDE(III)/ACTINIDE(III) DIFFERENTIATION; TETRAPYRROLE LIGANDS; CERIUM(IV) COMPLEXES; ELECTRONIC-STRUCTURE; SANDWICH COMPLEXES; CRYSTAL-STRUCTURE; METAL-COMPLEXES; ACTINIDE; DENSITY; OXIDATION;

D O I：

10.1002/chem.201001471

中图分类号：

O6 [化学];

学科分类号：

070301 [无机化学];

摘要：

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.

引用

页码：9623 / 9629

页数：7

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