Valence Charge Concentrations, Electron Delocalization and β‐Agostic Bonding in d 0 Metal Alkyl Complexes

• Published in: Chemistry : a European journal 2003-12, Vol.9 (24), p.6057-6070
• Main Authors: Scherer, Wolfgang, Sirsch, Peter, Shorokhov, Dmitry, Tafipolsky, Maxim, McGrady, G. Sean, Gullo, Emanuel
• Format: Article
• Language: English
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200304909

In this paper we describe a range of model d 0 metal ethyl compounds and related complexes, studied by DFT calculations and high resolution X‐ray diffraction. The concept of ligand‐opposed charge concentrations (LOCCs) for d 0 metal complexes is extended to include both cis ‐and trans ‐ligand‐induced charge concentrations (LICCs) at the metal, which arise as a natural consequence of covalent metal–ligand bond formation in transition metal alkyl complexes. The interplay between locally induced sites of increased Lewis acidity and an ethyl ligand is crucial to the development of a β‐agostic interaction in d 0 metal alkyl complexes, which is driven by delocalization of the MC bonding electrons. Topological analysis of theoretical and experimental charge densities reveals LICCs at the metal atom, and indicates delocalization of the MC valence electrons over the alkyl fragment, with depletion of the metal‐directed charge concentration (CC) at the α‐carbon atom, and a characteristic ellipticity profile for the C α C β bond. These ellipticity profiles and the magnitude of the CC values at C α and C β provide experimentally observable criteria for assessing quantitatively the extent of delocalization, with excellent agreement between experiment and theory. Finally, a concept is proposed which promises systematic control of the extent of CH activation in agostic complexes.