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The most attractive and fundamental interaction between metal centers and organic molecules that could lead to new functionalization at carbon is direct activation of the C-H bonds of hydrocarbons. In particular, transition metal complexes have been used not only in pioneering studies of the synthesis or detection of complexes resulting from C-H activation, but also in cyclometalation chemistry. In most of the reactions reviewed here intramolecular assistance by a nucleophile plays a major role in the mechanism and/or in the stabilization of products, and\udthus they are relevant also to the development of a\udbetter understanding of cyclometalation reactions.  This Account summarizes recent research that implicates the occurrence of electrophilic attack at the metal center in reactions leading to metal-electrophile bondin

Mechanisms of d8 organometallic reactions involving electrophiles and intramolecular assistance by nucleophiles