| Synthesis, spectral, and structural characterizations of imidazole oxalato molybdenum(iv/v/vi) complexes. | |
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MedLine Citation:
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PMID: 23143282 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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Substitutions of trans-Na(Him)[Mo(2)O(4)(ox)(2)(H(2)O)(2)]·H(2)O () and trans-(Him)(2)[Mo(2)O(4)(ox)(2)(H(2)O)(2)] () with imidazole result in the formation of the mixed-ligand molybdenum complexes cis-Na(2)[Mo(2)O(4)(ox)(2)(im)(2)]·4.5H(2)O (), cis-K(2)[Mo(2)O(4)(ox)(2)(im)(2)]·3H(2)O (), respectively (H(2)ox = oxalic acid; im = imidazole). Further reduction of cis-K(2)[Mo(2)O(4)(ox)(2)(im)(2)]·3H(2)O () gives a trinuclear molybdenum(iv) complex K(Him)[Mo(3)O(4)(ox)(3)(im)(3)]·3H(2)O (), which contains an incomplete cubane cluster [Mo(IV)(3)O(4)](4+). Two novel trinuclear mixed-valence imidazole compounds [Mo(3)O(8)(im)(4)](im)·H(2)O () and [Mo(3)O(8)(im)(4)]·H(2)O () were obtained by the reduction of (Him)(4)[Mo(8)O(26)(im)(2)] (). Both and contain a novel Mo(VI)O(4)(Mo(V)(2)O(4)) center, where the [Mo(V)(2)O(4)](2+) unit is linked by [Mo(VI)O(4)](2-) anion. The Mo-Mo bond distances in decrease with the decrease of oxidation state of molybdenum. Solid and solution NMR spectra show that imidazole molybdenum compounds fully dissociate in solution, where solvated imidazole and imidazolium groups in and could be served as internal references in their solid (13)C NMR spectra. Furthermore, mixed-ligand molybdenum species and are stable in water. Stabilities of and in solution may be attributed to the strong coordination of bidentate oxalate and the formation of hydrogen bond. Dimers and display quasi-reversible redox process, while trimer is irreversible. Bond valence calculations for are consistent with their oxidation states of molybdenum atoms. Calculation of the oxidation state in recent structure of iron molybdenum cofactor [MoFe(7)S(9)C(R-homocit)] (FeMo-co) is 3.318. |
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Authors:
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Quan-Liang Chen; Hong-Bin Chen; Ze-Xing Cao; Zhao-Hui Zhou |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-11-12 |
Journal Detail:
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Title: Dalton transactions (Cambridge, England : 2003) Volume: - ISSN: 1477-9234 ISO Abbreviation: Dalton Trans Publication Date: 2012 Nov |
Date Detail:
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Created Date: 2012-11-12 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101176026 Medline TA: Dalton Trans Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. zhzhou@xmu.edu.cn. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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