Some aspects of the bioinorganic chemistry of molybdenum
TL;DR: The biological role of molybdenum, biophysical studies of the molybordenum atoms, and aspects of coordination chemistry that bear on the understanding of Molybdo-enzymes are discussed in this paper.
Abstract: The biological role of molybdenum, biophysical studies of the molybdenum atoms in molybdo-enzymes, and aspects of coordination chemistry that bear on the understanding of molybdo-enzymes.
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TL;DR: In this paper, a molybdenum(0) carbonyl complex with multidentate organosulfur ligands was obtained from [Mo(CO) 3 (CH 3 CN) 3 ] and [MoCl 3 (TTCN] under regeneration of the starting complex.
40 citations
TL;DR: During the global transition to oxic conditions, reduced Mo species were constrained to specific anaerobic habitats, and efficient uptake systems of oxidized Mo(VI) became a selective advantage for current prokaryotic and eukaryotic cells.
Abstract: The transition element molybdenum (Mo) possesses diverse valances (+II to +VI), and is involved in forming cofactors in more than 60 enzymes in biology. Redox switching of the element in these enzymes catalyzes a series of metabolic reactions in both prokaryotes and eukaryotes, and the element therefore plays a fundamental role in the global carbon, nitrogen, and sulfur cycling. In the present oxygenated waters, oxidized Mo(VI) predominates thermodynamically, whilst reduced Mo species are mainly confined within specific niches including cytoplasm. Only recently has the reduced Mo(V) been separated from Mo(VI) in sulfidic mats and even in some reducing waters. Given the presence of reduced Mo(V) in contemporary anaerobic habitats, it seems that reduced Mo species were present in the ancient reducing ocean (probably under both ferrigenous and sulfidic conditions), prompting the involvement of Mo in enzymes including nitrogenase and nitrate reductase. During the global transition to oxic conditions, reduced Mo species were constrained to specific anaerobic habitats, and efficient uptake systems of oxidized Mo(VI) became a selective advantage both for prokaryotic and eukaryotic cells. Some prokaryotes are still able to directly utilize reduced Mo if any exists in ambient environments. In total, this mini-review describes the redox chemistry and biogeochemistry of Mo over the Earth’s history.
40 citations
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...With the protection, Mo can easily switch redox states, and be actively involved in transferring electron/proton and even oxygen (e.g., Swedo and Enemark, 1979)....
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TL;DR: The proposed novel and sensitive spectrophotometric method for the determination of molybdenum at trace levels in environmental and biological samples has been successfully applied and most of the metal ions tested did not interfere in the determination.
27 citations
TL;DR: The coordination of alloxazine and pterins to molybdenum(IV) is demonstrated in this paper, where the synthesis of MoOCl3(pteridineH), where pteridineH is the protonated form of 1,3,7,8-tetramethylalloxazine (tmaz), 2-pivaloyl-6,7-dimethylpterin (piv-dmp), and 6,7dimethylmidtin (dmp) proceeds readily starting from MoCl4(acetonitrile
Abstract: The coordination of alloxazine and pterins to molybdenum(IV) is demonstrated in this study. The synthesis of MoOCl3(pteridineH), where pteridineH is the protonated form of 1,3,7,8-tetramethylalloxazine (tmaz), 2-pivaloyl-6,7-dimethylpterin (piv-dmp), and 6,7-dimethylpterin (dmp), proceeds readily starting from Mo(IV)Cl4(acetonitrile)2 and the pteridine ligand in chloroform or methanol. X-ray crystal structures of MoOCl3(tmazH) (1) and MoOCl3(piv-dmpH) (2) show that Mo chelates each pteridine at the carbonyl oxygen and pyrazine nitrogen and that the pteridine ligand is protonated at the other nitrogen in the pyrazine ring. A third X-ray structure for MoOCl3(H3dmp) (4) is included in this work since its determination permits the comparison of metrical parameters for the oxidized and reduced forms of a pterin in identical molybdenum coordination environments. The major difference observed in the structures of 2 as compared to 4 is the Mo−N5 bond length which is significantly shorter in compound 4 containing ...
22 citations
TL;DR: In this article, a complexe avec la glycine cristallise dans P2 1 /c avec Z=4; R=0,022, 0.027
19 citations