title: Crystal structures and 77Se NMR spectra of molybdenum(IV) areneselenolates having intramolecular NH...Se hydrogen bonds.
abstract: Salts of the monooxomolybdenum(IV,V) areneselenolates having intramolecular NH...Se hydrogen bonds, [Mo(IV)O(Se-2-RCONHC6H4)4]2- (R = t-Bu, CH3, CF3) and [Mo(V)O(Se-2-t-BuCONHC6H4)4]-, were synthesized and characterized by 1H nuclear magnetic resonance (NMR), 77Se NMR, electron spin resonance (ESR), UV-visible spectra, X-ray analysis, and electrochemical measurements. 77Se-1H correlated spectroscopy (COSY) indicated a significant correlation between amide 1H and selenolate 77Se atoms through an NH...Se hydrogen bond with 1J(77Se-1H) = 5.4 Hz coupling. The hydrogen bonds contribute to the positive shift in the Mo(V)/Mo(IV) redox potential. In the crystal structure of (PPh4)2[Mo(IV)O(Se-2-CH3CONHC6H4)4], an NH...O=Mo hydrogen bond was found. Ab inito calculations support the presence of intramolecular NH...O=Mo and NH...Se hydrogen bonds.
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp
authors.forename: Taka-Aki
authors.initials: TA
authors.lastname: Okamura
authors.forename: Kaku
authors.initials: K
authors.lastname: Taniuchi
authors.forename: Keonil
authors.initials: K
authors.lastname: Lee
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Yamamoto
authors.forename: Norikazu
authors.initials: N
authors.lastname: Ueyama
authors.forename: Akira
authors.initials: A
authors.lastname: Nakamura
mesh_terms: D018360:Crystallography, X-Ray; D004563:Electrochemistry; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D012643:Selenium / Q000737:chemistry*; D012996:Solutions
chemical_list: D012996:Solutions; D006859:Hydrogen; D008982:Molybdenum; D012643:Selenium; D009584:Nitrogen