The effect of charge on CO binding in rhodium carbonyls: From bridging to terminal CO
Publication date
2008-02-20
Authors
Swart, Ingmar
de Groot, Frank
Weckhuysen, Bert
Rayner, David M.
Meijer, Gerard
Fielicke, Andre
Editors
Advisors
Supervisors
Document Type
Article
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Abstract
The structures of cabonic rhodium carbonyl cluster compounds containing one to six Rh atoms are established by infrared multiple photon dissociation spectroscopy. Comparison with their weld known neutral analogues reveals that ionization of the neutral compounds destabilizes bridge bound CO ligands in Rh-2(CO)(8) and Rh-4(CO)(12), leading to cationic complexes with only terminally bound CO. The destabilization is associated with removal of charge from a highest occupied molecular orbital that is banding with respect to bridge-bound CO. Density functional theory calculations support this conclusion. The results provide a possible insight into electronic promoter effects in catalysis.
Keywords
Clusters, Catalysts, Taverne
Citation
Swart, I, de Groot, F M F, Weckhuysen, B M, Rayner, D M, Meijer, G & Fielicke, A 2008, 'The effect of charge on CO binding in rhodium carbonyls : From bridging to terminal CO', Journal of the American Chemical Society, vol. 130, no. 7, pp. 2126-2127. https://doi.org/10.1021/ja0772795