Quantum Chemical Characterization of the Bonding of N-Heterocyclic Carbenes to Cp2MI Compounds [M = Ce(III), U(III)]

Gagliardi, Laura; Cramer, Christopher J.

doi:10.1021/ic061306v

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Title		Quantum Chemical Characterization of the Bonding of N-Heterocyclic Carbenes to Cp2MI Compounds [M = Ce(III), U(III)]
Authors		Gagliardi, Laura Cramer, Christopher J.
Published in		Inorganic Chemistry. 2006, vol. 45, no. 23, p. 9442-9447
Abstract		The binding of N-heterocyclic carbenes to Ce(III) and U(III) compounds is characterized by quantum chemical methods. Density functional methods are in qualitative agreement with experiment that binding to U(III) is more favorable than to Ce(III); after correcting for basis-set superposition error, quantitative agreement with experiment is achieved with a multireference second-order perturbation theory approach accounting for relativistic effects. The small computed (and observed) preference derives from a combination of several small effects, including differences in electronic binding energies, rovibrational partition functions, and solvation free energies. Prospects for ligand modification to improve the differentiation between lanthanides and actinides are discussed on the basis of computational predictions.
Identifiers		DOI: 10.1021/ic061306v
Full text		Article (Published version) - Free access Other version: http://pubs.acs.org/cgi-bin/article.cgi/inocaj/2006/45/i23/pdf/ic061306v.pdf
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie physique
Research group		Groupe Gagliardi
Citation (ISO format)		GAGLIARDI, Laura, CRAMER, Christopher J. Quantum Chemical Characterization of the Bonding of N-Heterocyclic Carbenes to Cp2MI Compounds [M = Ce(III), U(III)]. In: Inorganic Chemistry, 2006, vol. 45, n° 23, p. 9442-9447. doi: 10.1021/ic061306v https://archive-ouverte.unige.ch/unige:3296