Molybdenum(VI) Coordination Chemistry of the N,N-Disubstituted Bis(hydroxylamido)-1,3,5-triazine Ligand, H(2)bihyat. Water-Assisted Activation of the Mo-VI=O Bond and Reversible Dimerization of cis-[(MoO2)-O-VI(bihyat)] to [(Mo2O4)-O-VI(bihyat)(2)(H2O)(2)]

 
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2012 (EN)
Molybdenum(VI) Coordination Chemistry of the N,N-Disubstituted Bis(hydroxylamido)-1,3,5-triazine Ligand, H(2)bihyat. Water-Assisted Activation of the Mo-VI=O Bond and Reversible Dimerization of cis-[(MoO2)-O-VI(bihyat)] to [(Mo2O4)-O-VI(bihyat)(2)(H2O)(2)] (EN)

Stylianou, M. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Stylianou, M. (EN)

Reaction of the N,N-disubstituted bis(hydroxylamino) ligand 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H(2)bihyat) with cis-[(MoO2)-O-VI(acac)(2)] in tetrahydrofuran resulted in isolation of the mononuclear compound cis-[(MoO2)-O-VI(bihyat)] (1). The treatment of (Na2MoO4)-O-VI center dot 2H(2)O with the ligand H(2)bihyat in aqueous solution gave the dinuclear compounds cis-[(Mo2O4)-O-VI(bihyat)(2)(H2O)(2)] (2) and trans-[(Mo2O4)-O-VI(bihyat)(2)(H2O)(2)] (3) at pH values of 3.5 and 5.5, respectively. The structures for the three molybdenum(VI) compounds were determined by X-ray crystallography. Compound 1 has a square-pyramidal arrangement around molybdenum, while in the two dinuclear compounds, each molybdenum atom is in a distorted pentagonal-bipyramidal environment of two bridging and one terminal oxido groups, a tridentate (O,N,O) bihyat(2-) ligand that forms two five-membered chelate rings, and a water molecule trans to the terminal oxido group. The dinuclear compounds constitute rare examples containing the {(Mo2O2)-O-VI(mu(2)-O-2)}(4+) moiety. The potentiometry revealed that the Mo(VI)bihyat(2-) species exhibit high hydrolytic stability in aqueous solution at a narrow range of pH values, 3-5. A subtle change in the coordination environment of the five-coordinate compound 1 with ligation of a wealdy bound water molecule trans to the oxido ligand (1w) renders the equatorial oxido group in 1w more nucleophilic than that in 1, and this oxido group attacks a molybdenum atom and thus the dinuclear compounds 2 and 3 are formed. This process might be considered as the first step of the oxido group nucleophilic attack on organic substrates, resulting in oxidation of the substrate, in the active site of molybdenum enzymes such as xanthine oxidase. Theoretical calculations in the gas phase were performed to examine the influence of water on the dimerization process (1 -> 2/3). In addition, the molecular structures, cis/trans geometrical isomerism for the dinuclear molybdenum(VI) species, vibrational spectra, and energetics of the metal-ligand interaction for the three molybdenum(VI) compounds 1-3 have been studied by means of density functional theory calculations. (EN)

enhanced hydrolytic stability (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

Inorg Chem (EN)

English

2012

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