Document Detail


Synthesis, spectral, and structural characterizations of imidazole oxalato molybdenum(iv/v/vi) complexes.
MedLine Citation:
PMID:  23143282     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
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.
Authors:
Quan-Liang Chen; Hong-Bin Chen; Ze-Xing Cao; Zhao-Hui Zhou
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-12
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-11-12     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
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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