Journal article

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

Publication Details
Author(s): Alzoubi B, Weber I, Walther M, van Eikema Hommes N, Puchta R, van Eldik R
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.

How to cite
APA: 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.

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

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