Electronic Modification of a Reduced Mononuclear Nonheme Iron Nitrosyl Complex Leads to HNO Release.

ABSTRACT: A new pentadentate-fluorinated N₄S(thiolate) ligand was synthesized. Reaction with Fe(BF₄)₂·6H₂O gives a new thioether complex, [Fe^II(CH₃CN)(N3Py^pFSEtCN)][BF₄]₂ (1), and on-metal deprotection gives the thiolate complex, [Fe^II(CH₃CN)(N3Py^pFS)][BF₄] (2). Reaction of 2 with NO forms a low-spin ground state (S = 1/2) {FeNO}⁷ complex (3). Chemical reduction of 3 with cobaltocene gives a metastable intermediate spin S = 1 {FeNO}⁸ complex (4). Protonation of 4 releases nitroxyl (HNO), as observed by ESI-MS and ³¹P NMR trapping experiments with PPh₃. C

SUBMITTER: Wade JA 

PROVIDER: S-EPMC12805933 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature