Replacement of an oxo by an imido group in oxotransferase model compounds: influence on the oxygen atom transfer.
Treatment of [MoO(N-t-Bu)Cl(2)(dme)] (dme = dimethoxyethane) with 2 equiv of the potassium salts of Schiff base ligands of the type KArNC(CH(3))CHC(CH(3))O afforded oxo imido molybdenum(VI) compounds [MoO(N-t-Bu)L(2)] {1, with Ar = phenyl (L(Ph)), 2 with Ar = 2-tolyl (L(MePh)), 3 with Ar = 2,6-dimethylphenyl (L(Me2Ph)) and 4 with Ar = 2,6-diisopropylphenyl (L(iPr2Ph))}. We have also prepared related bisimido complexes [Mo(N-t-Bu)(2)L(2) (5 with L = L(Ph), 6 with L = L(MePh), and 7 with L = L(Me2Ph)) by treatment of [Mo(N-t-Bu)(2)Cl(2)(dme)] with 2 equiv of the potassium salt of the respective ligand. 1, 3, 5, and 6 were characterized via single crystal X-ray diffraction. The oxo imido complexes exhibit oxygen atom transfer (OAT) reactivity toward trimethyl phosphine. Kinetic data were obtained for 1 and 3 by UV/vis spectroscopy revealing decreased OAT reactivity in comparison to related dioxo complexes with the same Schiff base ligands and decreased reactivity of 1 versus 3. Cyclic voltammetry was used to probe the electronic situation at the molybdenum center showing reversible reduction waves for 3 and [MoO(2)(L(Me2Ph))(2)] at comparable potentials while 1 exhibits a significant lower potential. Density functional theory (DFT) calculations showed a higher electron density on oxygen in the oxo imido complexes.
Mösch-Zanetti
Nadia C
NC
Institut für Chemie, Karl-Franzens-Universität Graz, Schubertstrasse, 1 A-8010 Graz, Austria. nadia.moesch@uni-graz.at
Wurm
Dietmar
D
Volpe
Manuel
M
Lyashenko
Ganna
G
Harum
Bastian
B
Belaj
Ferdinand
F
Baumgartner
Judith
J
D004579:Electron Transport; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
D009942:Organometallic Compounds; D008982:Molybdenum; D010088:Oxidoreductases; D010100:Oxygen