Transition-metal nitrido complexes have long been of interest as putative intermediate species in various organic/inorganic transformations and in biological nitrogen fixation. Late transition metal species with metal-ligand multiple bonds are not common, and tend to be highly reactive, often serving as important intermediate species in reactions involving functionalization of organic substrates. Previous work has been successful at synthesizing a nickel complex, [CztBu(PyriPr)(NH2−PyriPr)], by irradiating a disphenoidal Ni(II) azido complex, [CztBu(PyriPr)2NiN3]. The present work seeks to expand the nickel complex research, and to substitute it with iron and cobalt, using Density Functional Theory (DFT), B3LYP/6-31+G(d’) to calculate the generation of an intermediate with significant nitridyl radical character after the loss of N2 from the starting azido complex. DFT and time-dependent density-functional theory (TDDFT) were also used to build a proposed detailed pathway for the reaction of the azido complex, [CztBu(PyriPr)2MN3] to form the amine complex [CztBu(PyriPr)M(NH2−PyriPr)], where M could be either cobalt, nickel or iron, comprised of intermediates of low, intermediate and high spin multiplicity and photo generated excited states.

DFT and TDDFT calculations on the reaction pathway of multiple intramolecular C-H functionalizations by iron, cobalt and nickel organometallic nitridyl complexes to form amine products

ACS Fall 2020 Virtual Meeting

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