Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand

Findlay, Neil and Park, Stuart Robert and Schoenebeck, Franziska and Cahard, Elise and Zhou, Sheng-Ze and Berlouis, Leonard and Spicer, Mark and Tuttle, Tell and Murphy, John (2010) Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand. Journal of the American Chemical Society, 132 (44). pp. 15462-15464. ISSN 0002-7863

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Abstract

The first crown-tetracarbene complex of Ni(II) has been prepared, and its crystal structure determined. The complex can be reduced by Na/Hg, with an uptake of two electrons. The reduced complex reductively cleaves arenesulfonamides, including those derived from secondary aliphatic amines, and effects Birch reduction of anthracenes as well as reductive cleavage of stilbene oxides. Computational studies show that the orbital that receives electrons upon reduction of the complex 2 is predominantly based on the crown carbene ligand and also that the HOMO of the parent complex 2 is based on the ligand.