While less common, metal ions are known to bind to protein backbone carboxamido nitrogens in metalloenzymes, forming metal-amidato bonds [M-NC(O)]. We are interested in gaining a better fundamental understanding of metal-amidato bonded systems through the use of direct-atom and atom-exchange synthetic analogue methods. This work used the atom-exchange method to prepare a model system for the distal nickel(II) center in the A-Cluster of carbon monoxide dehydrogenase/acetyl coenzyme-A synthase (CODH). The synthetic analogue prepared, a phosphorus-for-sulfur atom exchanged analogue, is a nickel(II) diamidato-bis(phosphine) complex. Herein we report our findings on the synthesis, structural characterization (including solution NMR and single crystal X-ray diffraction studies), and electrochemistry (cyclic voltammetry) of the synthetic analogue. Furthermore, we report on the reactivity of the complex under reducing conditions, including the preparation and characterization of an interesting orthometallated complex.

Atom-exchanged synthetic analog approach to metal-amidato system: Modeling the distal nickel center in the A-cluster of CODH

245th National Meeting (2013)

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