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Book ChapterDOI

The Coordination and Bioinorganic Chemistry of Molybdenum

09 Mar 2007-pp 1-223
About: The article was published on 2007-03-09. It has received 78 citations till now. The article focuses on the topics: Bioorganometallic chemistry & Bioinorganic chemistry.
Citations
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Journal ArticleDOI
TL;DR: The 2011 WHO Guidelines for Drinking-Water Quality (fourth edition) advised a health-based value of 70μg/L for Mo but this is no longer promulgated as a formal guideline value as WHO consider such concentrations to be rarely found in drinking water as discussed by the authors.

196 citations

Journal ArticleDOI
Russ Hille1
TL;DR: An overview of the current state of our understanding of the molybdenum-containing enzyme xanthine oxidoreductase is presented, with an emphasis on work done in the past five years.
Abstract: An overview of the current state of our understanding of the reaction mechanism of the molybdenum-containing enzyme xanthine oxidoreductase is presented, with an emphasis on work done in the past five years Recent studies of the biosynthesis of the pterin cofactor bound to the metal in the active site are also reviewed, as is crystallographic work that has clarified the coordination geometry of the molybdenum center This structural work provides the context in which to understand recent mechanistic studies of the enzyme, in particular those aimed at elucidating the role of specific amino acid residues in the active site of the enzyme(© Wiley-VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2006)

119 citations

Journal ArticleDOI
TL;DR: In this article, synthetic aspects of molybdenum sulfide-based materials were reviewed, with emphasis on the catalytic materials, and a number of preparation methods were critically compared, including molecular precursor decomposition, hydrothermal, soft chemistry aqueous, surfactant-aided, intercalation-exfoliation, and solid gas reactions.

114 citations

Journal ArticleDOI
TL;DR: The ability of Desulfovibrio desulfuricans formate dehydrogenase (DdFDH) to reduce carbon dioxide was kinetically and mechanistically characterized and a kinetic model of a hysteretic enzyme is proposed to interpret and predict the progress curves of the Dd FDH-catalyzed reactions.
Abstract: Carbon dioxide accumulation is a major concern for the ecosystems, but its abundance and low cost make it an interesting source for the production of chemical feedstocks and fuels. However, the thermodynamic and kinetic stability of the carbon dioxide molecule makes its activation a challenging task. Studying the chemistry used by nature to functionalize carbon dioxide should be helpful for the development of new efficient (bio)catalysts for atmospheric carbon dioxide utilization. In this work, the ability of Desulfovibrio desulfuricans formate dehydrogenase (Dd FDH) to reduce carbon dioxide was kinetically and mechanistically characterized. The Dd FDH is suggested to be purified in an inactive form that has to be activated through a reduction-dependent mechanism. A kinetic model of a hysteretic enzyme is proposed to interpret and predict the progress curves of the Dd FDH-catalyzed reactions (initial lag phase and subsequent faster phase). Once activated, Dd FDH is able to efficiently catalyze, not only t...

103 citations

Journal ArticleDOI
TL;DR: The mesoporous molecular sieve MCM-41 was covalently grafted with 3-aminopropyl trimethoxysilane (AmpMCM41) in this article.
Abstract: The mesoporous molecular sieve MCM-41 was covalently grafted with 3-aminopropyl trimethoxysilane to give aminopropyl modified MCM-41 (AmpMCM-41). Reaction of this material with furfural, pyrrolcarbaldehyde, 2-acetylpyrrol, 2-aminoacetophenone, salicylaldehyde and acetylacetone afforded the corresponding supported Schiff base ligands. Subsequent reaction with bis(acetylacetonato)dioxomolybdenum(VI) leads to various molybdenum complexes supported on MCM-41 through propyl chain spacer. Characterization of these materials was carried out with FT-IR, atomic absorption spectroscopy, powder X-ray diffraction (XRD) and BET nitrogen adsorption–desorption methods. The XRD and BET analyses revealed that textural properties of support were preserved during the grafting experiments. The resultant materials successfully catalyzed the epoxidation of cyclooctene, cyclohexene, 1-hexene and 1-octene with tert -butyl hydroperoxide (TBHP) to the corresponding epoxides with 98–100% selectivities.

92 citations

References
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Journal ArticleDOI
TL;DR: In this article, the synthesis of thiocyanates of pentavalent molybdenum and hexavalent tungsten by reaction of molydenum pentachloride and tungstens hexachlorides or tengsten oxychloride with alkali thiocalinates in dry organic solvents is described.
Abstract: Die Darstellung von Thiocyanaten des funfwertigen Molybdans und des sechswertigen Wolframs durch Umsetzung von Molybdanpentachlorid bzw. Wolframhexachlorid oder Wolframoxidtetrachlorid mit Alkalithiocyanaten in wasserfreien organischen Losungsmitteln wird beschrieben. The synthesis of thiocyanates of pentavalent molybdenum and hexavalent tungsten by reaction of molybdenum pentachloride and tungsten hexachloride or tungsten oxychloride, respectively, with alkali thiocyanates in dry organic solvents is described.

10 citations

Journal ArticleDOI
TL;DR: In this paper, the results of SCCC MO calculations for the dimeric oxygen double-bridged [Mo2O4Cl4(H2O)2−ion are reported.
Abstract: Results of SCCC MO calculations for the dimeric oxygen double-bridged [Mo2O4Cl4(H2O)2]2−ion are reported. On the basis of these results the previously reported spectra and magnetic properties may be explained. The strong direct molybdenum — molybdenum interaction in the Mo2O 4 2+ core was proved to exist.

10 citations

Journal ArticleDOI
TL;DR: Tungsten(VI) oxide tetrachloride reacts with pentane 2,4-dione to form a salt whose single crystal X-ray structure shows a dichloro-dioxopentane-2,4dionato-tungsten (VI) anion and a 2.4,6-trimethyl-3-acetyl-pyrylium cation as mentioned in this paper.
Abstract: Tungsten(VI) oxide tetrachloride reacts with pentane-2,4-dione to form a salt whose single crystal X-ray structure shows a dichloro-dioxopentane-2,4-dionato-tungsten(VI) anion and a 2,4,6-trimethyl-3-acetyl-pyrylium cation; the analogus reaction with molybdenum(VI) oxide tetrachloride yields 1,3,5,7-tetramethyl-2,4,6,8-tetraoxa-adamantane.

10 citations

Journal ArticleDOI
TL;DR: X-ray crystal studies of MoO2(C9H6NO)2 reveal that the O-Mo-O group has the cis-configuration as mentioned in this paper, which is the first known property of the MoO group.
Abstract: X-Ray crystal studies of MoO2(C9H6NO)2 reveal that the O–Mo–O group has the cis-configuration.

10 citations

Journal ArticleDOI
TL;DR: In the presence of excess of nitrite ion the complex [MoOCl3(OPPh3)2] is completely oxidised to MoVI in CH2Cl2.
Abstract: In the presence of excess of nitrite ion the complex [MoOCl3(OPPh3)2] is completely oxidised to MoVI in CH2Cl2. The reaction proceeds by three observable stages. Data for the first stage correspond to co-ordination of nitrite at molybdenum(V), via a limiting SN1 mechanism, involving loss of a triphenylphosphine oxide molecule. At 25 °C, k1= 51·8 ± 2·1 s–1, ΔH1‡= 12·6 ± 0·3 kcal moh–1, and ΔS1‡=–8·2 ± 1·0 cal K–1 mol–1. The data for the second stage of reaction are taken to indicate chelation and/or isomerisation of co-ordinated nitrito-ligand into a position cis to the oxo-group, followed by rapid non-rate-determining electron transfer. The third and final stage of reaction appears to involve co-ordination of the available nitrite to the primary molybdenum(VI) product, and subsequent rearrangement of these molybdenum(VI) products.

10 citations