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Effects of relativity on the NiCO, PdCO, and PtCO bonding mechanism: a constrained space orbital variation analysis of density functional results

✍ Scribed by Sai-Cheong Chung; Sven Krüger; Sergey Ph. Ruzankin; Gianfranco Pacchioni; Notker Rösch

Publisher: Elsevier Science
Year: 1996
Tongue: English
Weight: 557 KB
Volume: 248
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(95)01273-7

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✦ Synopsis

Using a density functional based constrained space orbital variation technique, we have analyzed the importance of relativistic effects on the various mechanisms which affect the metal-CO bond in Ni, Pd, and Pt monocarbonyls. The bonding is dominated by the ~r back-donation mechanism which, for Pd and Pt, is considerably reinforced by relativistic effects. The weaker Pd-CO bonding is rationalized by reduced back-donation. The combined effect of relativistic bond length contraction and of the atomic d orbital energies determines the trend in the metal-CO bond strengths. This trend is different from the one found for the coordinatively saturated M(CO) 4 tetracarbonyls.