A wealth of knowledge exists for metal-metal bonded complexes of the 2nd and 3rd row transition metals. In contrast, our understanding of these interactions within the late 1st row transition metals is limited.  To address this gap we have endeavored to synthesized metal-metal bonded complexed supported by ketimide co-ligands. Thus, addition of 2.5 equiv of Li(N=CtBu2) to MCl2 (M = Mn, Fe, Co), followed by the addition of 12-crown-4, yields the dimeric metal complexes [Li(12-crown-4)2][M2(N=CtBu2)5] (M = Mn (1 ), Fe (2 ), Co (3 )) in good yields. All three complexes have been fully characterized using NMR spectroscopy, electrochemistry, SQUID magnetometry, and X-ray crystallography.  All three structures exhibit the same core geometry consisting of two co-facial MN4 tetrahedra.  These complexes also exhibit short metal-metal distances, suggesting a direct metal-metal bond. This interaction is supported by bulk magnetization experiments which reveals strong antiferromagnetic coupling between the metal centers in all three complexes.

Synthesis and characterization of first row transition metal ketimides with supported metal-metal bonds

243rd National Meeting (2012)

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