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.
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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
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
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
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
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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TL;DR: In this article, the authors studied the absorbance of solutions at 450 mμ where the molar extinction changes from 12·6 for MoOCl52− to 2200 for the dimer at this wavelength.
49 citations
49 citations
TL;DR: In this paper, it was shown that for bivalent metals and with bidentate ligands co-ordination of carbonyl groups to the metal should lead preferentially to cis-octahedral structures.
Abstract: Reactions of several metal carbonyls with chelating ligands containing active protons have been carried out. The reactions of hexacarbonylchromium and hexacarbonylmolybdenum with N-methylsalicylideneimine led to the formation of the corresponding N-methylsalicylideneiminato-complexes of chromium(III) and molybdenum(III). These are most probably monomeric octahedral complexes as suggested by the magnetic moments which are somewhat lower than the spin-only value, as expected for a d3 octahedral configuration. Reactions of decacarbonyldimanganese with NN′-ethylenebis(salicylideneimine), SaEnH2, and with NN′-trimethylenebis(salicylideneimine) yielded the corresponding manganese(II) complexes; the NN′-trimethylenebis(salicylideneiminato)-derivative was found to absorb one mol. of oxygen as previously announced but no confirmation could be found of a similar absorption of molecular nitrogen. Pentacarbonyliron and SaEnH2 gave the air-sensitive FeSaEn together with some reaction by-products which were not fully identified. FeSaEn is a high-spin compound of d6 configuration and is converted by molecular oxygen into the µ-oxo-iron(III) derivative. If the trans-effect is of some importance in octahedral complexes, it seems that for bivalent metals and with bidentate ligands co-ordination of carbonyl groups to the metal should lead preferentially to cis-octahedral structures, whereas with quadridentate planar ligands the co-ordination of two carbonyl groups, necessarily occupying trans-positions, is probably not very likely to occur. These ideas have been tested with ruthenium and found to be reasonably well confirmed. Dodecacarbonyltriruthenium and acetylacetone, acacH, give the first example of a bis(acetylacetonato)carbonyl derivative, namely cis-Ru(acac)2(CO)2. Dodecacarbonyltriruthenium and the Schiff's base N-phenylsalicylideneimine, Ph–SaEnH, gave cis-Ru(Ph–SaEn)2(CO)2, a rather labile complex in polar solvents. Dodecacarbonyltriruthenium and SaEnH2 gave a very robust compound of probable formula RuSaEn,CO; a dimeric structure with terdentate oxygens has been suggested for this complex. Octacarbonyldicobalt and SaEnH2 gave CoSaEn in dimethylformamide. Octacarbonyldicobalt and NN′-ethylenebis(acetylacetoneimine), acacimH2, by gentle heating in heptane gave the tetracarbonylcobaltate [Co(acacimH2)3][Co(CO)4]2. The cobalt(II) derivative Co acacim reacts promptly with nitric oxide to give the nitrosyl derivative Co acacim NO.
49 citations
48 citations