title: The role of three-center/four-electron bonds in superelectrophilic dirhodium carbene and nitrene catalytic intermediates.
abstract: 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) σ and π bonds. These 3c/4e bonding interactions set apart dirhodium carbene and nitrene intermediates from other, less electrophilic, carbene or nitrene species.
authors: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
authors: John F
authors: JF
authors: Berry
mesh_terms: D002384:Catalysis; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry; D007097:Imines / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008962:Models, Theoretical; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*
chemical_list: D007097:Imines; C030011:carbene; C017621:phenylnitrene; D006859:Hydrogen; D012238:Rhodium; D008697:Methane