Spin-state crossover in photo-catalyzed nitrile dihydroboration via Mn-thiolate cooperation

The role of S-donors in ligand-assisted catalysis using first-row metals has not been broadly investigated. Herein is described a combined experimental and computational mechanistic study of the dihydroboration of nitriles with pinacolborane (HBpin) catalyzed by the Mn(i) complex, Mn(κ³-S^MeNS)(CO)₃, that features thioether, imine, and thiolate donors. Mechanistic studies revealed that catalysis requires the presence of UV light to enter and remain in the catalytic cycle and evidence is presented for loss of two CO ligands. Stoichiometric reactions showed that HBpin reduces the imine N[double bond, length as m-dash]C of the ligand backbone in the absence of nitrile, forming an inactive off-cycle by-product. DFT calculations showed that the bifunctional thiolate donor, coordinative flexibility of the S^MeNS ligand, and access to an open-shell intermediate are all crucuial to accessing low-energy intermediates during catalysis.