HCN exchange on [Cu(HCN)(4)](+): a quantum chemical investigation

Journal article

Publication Details

Author(s): Alzoubi B, Weber I, Walther M, van Eikema Hommes N, Puchta R, van Eldik R
Journal: Journal of Coordination Chemistry
Publisher: Taylor & Francis: STM, Behavioural Science and Public Health Titles / Taylor & Francis
Publication year: 2014
Volume: 67
Journal issue: 13
Pages range: 2185-2194
ISSN: 0095-8972


Density functional (B3LYP, B3PW91, X3LYP, BP86, PBEPBE, PW91PW91, and M06) and ab initio (MP2, MP4sdq, CCSD, and CCSD(T)) calculations with extended basis sets (6-311+G**, TZVP, LANL2DZ+p, and SDD+p, the latter including extra polarization and diffuse functions) indicate that HCN exchange on [Cu(HCN)(4)](+) proceeds via an associative interchange (I-a) mechanism and a D-3h transition structure {[Cu(HCN)(5)](+)}double dagger. The activation barrier, relative to the model complex [Cu(HCN)(4)](+)center dot HCN, varies modestly, depending on the computational level. Typical values are 8.0 kcalM(-1) (B3LYP/6-311+G**), 6.0 kcalM(-1) (M06/6-311+G**), and 4.8 kcalM(-1) (CCSD(T)/6-311+G**//MP2(full)/6-311+G**). Inclusion of an implicit solvent model (B3LYP(CPCM)/6-311+G**) leads to an activation barrier of 5.8 kcal mol(-1). Comparison of the HCN exchange mechanisms on [Li(HCN)(4)](+)(limiting associative, A) and [Cu(HCN) (4)](+)(associative interchange, I-a) reveals that pi back donation in the equatorial Cu-N bonds in the transition state determines the mechanism.

FAU Authors / FAU Editors

Puchta, Ralph PD Dr.
Naturwissenschaftliche Fakultät
van Eikema Hommes, Nico Dr.
van Eldik, Rudi Prof. Dr.
Naturwissenschaftliche Fakultät
Walther, Markus
Professur für Theoretische Chemie
Weber, Immo Dr.
Lehrstuhl für Anorganische und Metallorganische Chemie

How to cite

Alzoubi, B., Weber, I., Walther, M., van Eikema Hommes, N., Puchta, R., & van Eldik, R. (2014). HCN exchange on [Cu(HCN)(4)](+): a quantum chemical investigation. Journal of Coordination Chemistry, 67(13), 2185-2194. https://dx.doi.org/10.1080/00958972.2014.941828

Alzoubi, Basam, et al. "HCN exchange on [Cu(HCN)(4)](+): a quantum chemical investigation." Journal of Coordination Chemistry 67.13 (2014): 2185-2194.


Last updated on 2018-29-06 at 09:23