{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["13(42)"],"submitter":["Elsby MR"],"pubmed_abstract":["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(κ<sup>3</sup>-S<sup>Me</sup>NS)(CO)<sub>3</sub>, 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 thiol"],"journal":["Chemical science"],"pagination":["12550-12559"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9629026"],"repository":["biostudies-literature"],"pubmed_title":["Spin-state crossover in photo-catalyzed nitrile dihydroboration <i>via</i> Mn-thiolate cooperation."],"pmcid":["PMC9629026"],"pubmed_authors":["Baik MH","Kim SYH","Elsby MR","Oh C","Son M","Baker RT"],"additional_accession":[]},"is_claimable":false,"name":"Spin-state crossover in photo-catalyzed nitrile dihydroboration <i>via</i> Mn-thiolate cooperation.","description":"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(κ<sup>3</sup>-S<sup>Me</sup>NS)(CO)<sub>3</sub>, 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 thiol","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Nov","modification":"2025-04-21T23:40:46.296Z","creation":"2025-04-05T19:13:18.783Z"},"accession":"S-EPMC9629026","cross_references":{"pubmed":["36382284"],"doi":["10.1039/d2sc04339d"]}}