Carbon monoxide (CO) is an attractive C1 building block to access hydrocarbons, but there are no homogeneous catalysts capable of generating hydrocarbons from CO. In contrast, the nitrogenase enzyme has been shown to catalyze the reductive coupling of CO to yield ethane, ethylene, and propane under mild conditions. To develop a mechanistic understanding of nitrogenase, we have synthesized several iron(II) complexes as structural mimics of the enzyme active site, and in our initial studies, isocyanides have been used as models for CO. A series of iron(II) hydrotris(mercaptoimidazolyl)borate isocyanide complexes of the general composition [Fe(TmR)(CNR')n](OTf) (where  Tm= hydrotris(mercaptoimidazolyl)borate, R= Me, Ph, o-toly, tert-butyl; R'= benzyl, cyclohexyl, tert-butyl; n= 1,2,3; and OTf= trifluoromethanesulfonate) were synthesized and characterized. The reactivity of the above complexes in the presence of a strong reductant such as cobaltocene and a proton source such as lutidinium chloride will be discussed.

Synthesis and reactivity of new iron hydrotris(mercaptoimidazolyl)borate complexes for the reductive coupling of carbon monoxide and isocyanides

248th National Meeting (2014)

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