Browsing by Author "Gun, J"
Now showing 1 - 3 of 3
Results Per Page
Sort Options
Item High oxidation state aqueous organometallics.: Formation and structure of an oxo-centred Cp* MoV trinuclear cation by chemical reduction of Cp*2Mo2O5Demirhan, F; Gun, J; Lev, O; Modestov, A; Poli, R; Richard, PReduction of Cp*2Mo2O5 by zinc/CF3CO2H in MeOH-H2O yields a salt which is composed of [Cp*3Mo3O4 (O2CCF3)(3)](+) and [Zn-2(O2CCF3)(6)](2-) ions after crystallisation from THF-Et2O.Item Reduction of [CP*2Mo2O5] by mercaptopropionic acid in an aqueous medium. Isolation and characterization of a dinuclear oxo- and 3-sulfido-proprionato(2-)-bridged molybdenum(IV) compoundDinoi, C; Prikhodchenko, P; Demirhan, F; Gun, J; Lev, O; Daran, JC; Poli, RReaction of Cp-2*Mo2O5 with HSCH2CH2COOH in acidic (by CF3COOH) 50:50 MeOH-H2O solvent at room temperature yields compound Cp-2*Mo-2(mu-O)(mu-SCH2CH2CO2)(2), a dinuclear diamagnetic Mo-IV compound with a two-leg-sharing bis(four-legged piano stool) structure and a Mo-Mo distance of 2.6833(6) angstrom. A reaction monitoring by ESI MS shows the formation of an intermediate 18 mass units heavier, interpreted as a dihydroxo analogue. Electrochemistry shows a reversible, pH independent oxidation process and an irreversible, pH-dependent reduction process. Contrary to a recently published analogous reaction with the closely related HSCH2COOH substrate, this process does not lead to C-S bond cleavage. (c) 2007 Elsevier B.V. All rights reserved.Item Aqueous reduction of [Cp*2W2O51]: Characterization of the triangular clusters [Cp*3W3O4(OH)2]2+ and [Cp*3W3O6]+ - Comparison with molybdenumDinoi, C; Sözen, P; Taban, G; Dernir, D; Demirhan, F; Prikhodchenko, P; Gun, J; Lev, O; Daran, JC; Poli, RZinc reduction Of CP * 2W2O5 in an acidified water-methanol medium affords the green 3-electron trinuclear cluster [CP*3W3O4(OH)(2)](+2), isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2-electron cluster, [Cp * 3W3O6], which was crystallized and characterized in three different salts, 2-4. The 3-electron cluster exhibits a near-tetragonal frozen-glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two-electron cluster is diamagnetic. An electro-spray ionization MS' study revealed a stepwise expulsion of neutral [CP*WO2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.