title: {Fe(NO)(2)(9) Dinitrosyl Iron Complex Acting as a Vehicle for the NO Radical.
abstract: To carry and deliver nitric oxide with a controlled redox state and rate is crucial for its pharmaceutical/medicinal applications. In this study, the capability of cationic {Fe(NO)2}9dinitrosyl iron complexes (DNICs) [(RDDB)Fe(NO)2]+(R = Me, Et, Iso;RDDB = N,N'-bis(2,6-dialkylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene) carrying nearly unperturbed nitric oxide radical to form [(RDDB)Fe(NO)2(•NO)]+was demonstrated and characterized by IR, UV-vis, EPR, NMR, and single-crystal X-ray diffractions. The unique triplet ground state of [(RDDB)Fe(NO)2(•NO)]+results from the ferromagnetic coupling between two strictly orthogonal orbitals, one from Fe dz2and the other a π*oporbital of a unique bent axial NO ligand, which is responsible for the growth of a half-field transition (ΔMS= 2) from 70 to 4 K in variable-temperature EPR measurements. Consistent with the NO radical character of coordinated axial NO ligand in complex [(MeDDB)Fe(NO)2(•NO)]+, the simple addition of MeCN/H2O into CH2Cl2solution of complexes [(RDDB)Fe(NO)2(•NO)]+at 25 °C released NO as a neutral radical, as demonstrated by the formation of [S5Fe(NO)2]-from [S5Fe(μ-S)2FeS5]2-.
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Chun-Hung
authors.initials: CH
authors.lastname: Ke
authors.affiliation: Department of Medical Applied Chemistry, Chung Shan Medical University, and Department of Medical Education, Chung Shan Medical University Hospital , Taichung 40201, Taiwan.
authors.forename: Chien-Hong
authors.initials: CH
authors.lastname: Chen
authors.affiliation: Department of Chemistry, National Sun Yat-sen University , Kaohsiung 80424, Taiwan.
authors.forename: Ming-Li
authors.initials: ML
authors.lastname: Tsai
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Hsuan-Chi
authors.initials: HC
authors.lastname: Wang
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Fu-Te
authors.initials: FT
authors.lastname: Tsai
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Yun-Wei
authors.identifier: 0000-0002-2101-8918
authors.initials: YW
authors.lastname: Chiang
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Wei-Chih
authors.initials: WC
authors.lastname: Shih
authors.affiliation: Department of Chemistry, McGill University 801 Sherbrooke Street West, Montreal, Quebec H3A2K6, Canada.
authors.forename: D Scott
authors.initials: DS
authors.lastname: Bohle
authors.affiliation: Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters, National Tsing Hua University , Hsinchu 30013, Taiwan.
authors.forename: Wen-Feng
authors.identifier: 0000-0001-9949-8344
authors.initials: WF
authors.lastname: Liaw
mesh_terms: D005609:Free Radicals / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008968:Molecular Conformation; D009569:Nitric Oxide / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D005609:Free Radicals; D009589:Nitrogen Oxides; D009569:Nitric Oxide; C073661:dinitrosyl iron complex; D007501:Iron