Complexes [(L)M(NCCH3)3](BF4)n (L = tris{3,5-dimethylpyrazol-1-yl}methane, TpmMe,Me, M = Mn, Fe, Co, Ni, n = 2; L = tris{3-phenylpyrazol-1-yl}methane, TpmPh, M = Mn, Fe, Co, Ni, n = 2; L = hydrotris{3,5-dimethylpyrazol-1-yl}borate, TpMe,Me, M = Fe, Co, Ni, n = 2; L =  hydrotris{3-phenyl-5-methylpyrazol-1-yl}borate, TpPh,Me, M = Mn, Co, Fe, Ni, n = 1) were prepared and characterized.  These complexes were utilized as catalysts for nitrene transfer from phenyl-N-tosyliminoiodinane (i.e., PhINTs) to a variety of organic substrates, resulting in olefin aziridination and C-H bond amination with varying degrees of efficiency.  A wide range organic products was obtained and fully characterized, and reaction mechanisms were probed with Hammett and kinetic isotope effects.  Insights into catalyst optimization will be discussed.

Nitrene transfer catalysis mediated by transition metal scorpionate complexes

244th National Meeting (2012)

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