Monomeric metal-thiolate complexes of formula Cp*M(1,2-Ph2PC6H4S) (M = Fe, 1; Co, 2) have been synthesized and structurally characterized. Our studies show that compound 1 is able to catalyze hydroboration of aryl epoxides and N-heteroarenes by pinacolborane, while 2 is an efficient catalyst for radical cyclization of 2-isocyanobiphenyls for building large p-conjugated N-heteroarenes. The scope and mechanisms of these reactions have been examined. In the catalytic hydroborations, the cooperative iron-thiolate catalyst directly activates the epoxide instead of the H-B bond of HBpin, and the coordination of N-heteroarenes to the iron center was also found to initiate the catalysis. The thiolate ligand in 2 can stabilize the metal center in a 17-electron configuration that enables this Co(II)-based metalloradical system for isocyanides activation.

Exploring iron and cobalt-based metal-thiolate catalysts for organic synthesis

255th National Meeting (2018)

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