Nature of β-Agostic Bonding in Late-Transition-Metal Alkyl Complexes

Experimental charge density analyses reveal significant differences between the nature of β‐agostic bonding in early‐ and late‐transition‐metal (M) complexes. For dn‐configurated M alkyl compounds, the β‐agostic interaction can be described by a modified Dewar–Chatt–Duncanson model with three σ/π bonding components, whereas one delocalized orbital is sufficient to account for the hyperconjugative stabilization in agostic d0 systems.