Hydrogen cyanide exchange on IAl(HCN)6]3+ - A DFT study

Puchta R, Alzoubi B, van Eldik R (2009)

Publication Type: Journal article

Publication year: 2009

Journal

Zeitschrift für Anorganische und Allgemeine Chemie Wiley

Book Volume: 635

Pages Range: 434-438

Journal Issue: 3

DOI: 10.1002/zaac.200801246

Abstract

The hydrogen cyanide exchange mechanism of [A1(HCN)6] 3+ has been investigated by DFT calculations (B3LYP/6-311 + G **). The calculations provide theoretical evidence that the hydrogen cyanide exchange proceeds via a limiting dissociative (D) mechanism involving a stable five-coordinate intermediate [A1(HCN)5· (HCN)2]3+. The activation energy for the D-mecha-nism is 23.4 kcal · mol-1, which is 2.8 kcal·mol-1 lower than for the seven-coordinate transition state [A1(HCN)2] 3+‡ for the alternative associative (A) pathway. The difference in stability between the two intermediates [A1(HCN)5 · (HCN)2]3+ (12.1 kcal · mol-1) and [A1(HCN)7]3+ (25.7 kcal · mol-1) in comparison to [A1(HCN)6 · (HCN)]3+ is much more pronounced and further supports a limiting dissociative mechanism. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

Authors with CRIS profile

Ralph Puchta Lehrstuhl für Anorganische und Metallorganische Chemie Rudi van Eldik Naturwissenschaftliche Fakultät

How to cite

APA:

Puchta, R., Alzoubi, B., & van Eldik, R. (2009). Hydrogen cyanide exchange on IAl(HCN)6]3+ - A DFT study. Zeitschrift für Anorganische und Allgemeine Chemie, 635(3), 434-438. https://doi.org/10.1002/zaac.200801246

MLA:

Puchta, Ralph, Basam Alzoubi, and Rudi van Eldik. "Hydrogen cyanide exchange on IAl(HCN)6]3+ - A DFT study." Zeitschrift für Anorganische und Allgemeine Chemie 635.3 (2009): 434-438.

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