The controlled activation of readily available but inert substrates (such as hydrocarbons, dihydrogen, etc.) could potentially lead to a more efficient and sustainable use of limited natural resources. Rare and expensive precious metals are common components of catalytic systems, and this limits their contribution to the value added product synthesis. The replacement of precious metals by the reactive complexes of the earth-abundant metals would address these challenges and have important implications for catalysis and green chemistry. The presentation is focused on the development of the earth-abundant metal catalysts, which reactivity strongly depends on the supporting ligand framework electronic properties and steric requirements. The use of sterically encumbered carboranyl clusters as ligands lead to the preparation of the catalytically active complexes of earth-abundant transition metals. The unique non-uniformity of the electronic distribution in icosahedral carboranes dramatically affects the electronic structure of the metal center. The metalated carboranyl systems were found to posses increased reactivity towards electrophiles due to cooperative effects caused by a high nucleophilicity of exohedral boron-metal bonds and significant B-H-M agostic interactions. The synthesis, structure, and reactivity of the carboranyl complexes of nickel, iron, and cobalt will be reported.

Carborane clusters in metal-ligand cooperative substrate activation.

249th National Meeting (2015)

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