Two-electron reduction of the tris(phosphinoamide)-linked early/late heterobimetallic complex ClZr(MesNPiPr2)3CoI leads to the metal-metal multiply bonded reduced complex (THF)Zr(MesNPiPr2)3CoN2. In addition to its highly reduced nature, the latter complex features labile ligands at both the Zr and Co ends of the molecule, predisposing this complex for reactivity with a wide variety of small molecule and organic substrates. In many cases substrates add across the metal-metal bond, but one-electron homolytic Zr-Co bond cleavage also occurs under certain conditions, resulting in radical-based reactivity at the Zr end of the molecule reminiscent of that expected for Zr(III). Such reactivity towards substrates such as alcohols, water, hydrazines, and ketones will be discussed along with the catalytic applications of these s-bond activation processes.

Effects of metal-metal interactions in Zr/Co heterobimetallic complexes on the reactivity at Zr

245th National Meeting (2013)

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