The role of three-center/four-electron bonds in superelectrophilic dirhodium carbene and nitrene catalytic intermediates

Three-center/four-electron (3c/4e) bonds are important bonding motifs that dictate the electronic structure{,} and thereby the reactivity{,} of metal-metal bonded carbene and nitrene intermediate complexes that are crucial to the dirhodium-catalyzed functionalization of hydrocarbons. In this Perspective article{,} general features of the 3c/4e bond are presented and discussed in comparison to two-center/two-electron (2c/2e) bonds. Specifically{,} 3c/4e bonding interactions lead to longer distances between the atoms involved and measurably weaker bonds. Additionally{,} excited states derived from the 3c/4e bonding manifold are lower in energy than those derived from a 2c/2e manifold{,} signifying a greater degree of reactivity in the former case. Three coterminous 3c/4e Ru-Ru-N bonds are present in metal-metal/metal-ligand multiply bonded diruthenium terminal nitrido compounds. This bonding situation results in an unusual superelectrophilic character of the nitride nitrogen atom{,} exemplified by its insertion into aryl C-H bonds via an electrophilic aromatic substitution mechanism. The key catalytic intermediates in dirhodium-catalyzed C-H functionalization reactions{,} dirhodium carbene and dirhodium nitrene complexes{,} may also be described as superelectrophilic by virtue of 3c/4e Rh-Rh-C(or N) [sigma] and [small pi] bonds. These 3c/4e bonding interactions set apart dirhodium carbene and nitrene intermediates from other{,} less electrophilic{,} carbene or nitrene species.

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