Ambidentate phosphinoamide ligands [R2PNR']- have  been utilized to supported metal-metal interactions in early/late  heterobimetallic complexes. The highly polar metal-metal interactions in  these species have been shown to have a drastic effect on redox  potentials, best exemplified by a ~1 V shift of the two-electron CoI/Co-I in a complex in which Co is in close proximity to a Lewis acidic Zr  center.  Upon two-electron reduction, heterobimetallic Co/Zr complexes  featuring unusual coordinatively unsaturated geometries and metal-metal  multiple bonds are afforded. These highly reactive complexes react under  ambient conditions with a variety of small molecule substrates,  including alkyl halides and H2.  These facile alkyl halide activation processes have led to the investigation of cross-coupling reactions and the unusual bimetallic mechanism involved. Recently, some very interesting E-H bond activation reactions (E = N, S, O) have been uncovered, and a discussion of the factors that dictate the mechanisms by which these s bond activation processes occur will be discussed.

Activation and functionalization of sigma bonds by early/late heterobimetallic complexes

243rd National Meeting (2012)

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