title: Thermodynamics of hydrogen atom transfer to a high-valent iron imido complex.
abstract: Thermodynamic investigations relevant to hydrogen atom transfer by the high-valent iron imido complex [LMesFe[triple bond]NAd]OTf have been undertaken. The complex is found to be weakly oxidizing by cyclic voltammetry (E1/2 = -0.98 V vs Cp2Fe+/Cp2Fe in MeCN). A combination of experimental and computational studies has been used to determine the acidity of LMesFe-N(H)Ad+ (pKa = 37 in MeCN), allowing the N-H BDFE (88(5) kcal/mol) to be calculated from a thermodynamic cycle. Consistent with this value, [LMesFe[triple bond]NAd]OTf reacts with 9,10-dihydroanthracene (C-H BDE = 78(1) kcal/mol) to form anthracene.
authors.affiliation: Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces New Mexico 88003, USA.
authors.forename: Ismael
authors.initials: I
authors.lastname: Nieto
authors.forename: Feizhi
authors.initials: F
authors.lastname: Ding
authors.forename: Ranko P
authors.initials: RP
authors.lastname: Bontchev
authors.forename: Haobin
authors.initials: H
authors.lastname: Wang
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Smith
mesh_terms: D018360:Crystallography, X-Ray; D004579:Electron Transport; D006859:Hydrogen / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008698:Mesylates / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D007094:Imides; D008024:Ligands; D008698:Mesylates; D009942:Organometallic Compounds; D006859:Hydrogen; D007501:Iron; C012077:trifluoromethanesulfonic acid