| Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2] |
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| 引用本文： | 鲁晓明 宋富根 娄福艳 毛希安 叶朝辉 卢景芬. Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2][J]. 中国化学, 2003, 21(11): 1474-1477. DOI: 10.1002/cjoc.20030211116 |
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| 作者姓名： | 鲁晓明 宋富根 娄福艳 毛希安 叶朝辉 卢景芬 |
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| 作者单位： | [1]DepartmentofChemistry,CapitalNormalUniversity,Beijing100037,China [2]WuhanInstituteofPhysicsandMathematics,ChineseAcademyofSciences,Wuhan,Hubei430071,China [3]StateKeyLaboratoryofNaturalandBiomimeticDrugs,MedicineScienceCenter,PekingUniversity,Beijing100083,China |
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| 基金项目： | ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 2 710 3 4) ,theNaturalScienceFoundationofBeijing(No .2 0 12 0 0 5 )andtheNaturalScienceFoundationofEducationalMinistryofBeijing |
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| 摘 要： | Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.
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| 关 键 词： | 合成 晶体结构 UV-vis分析 EPR分析 X-射线衍射分析 （NH3CH2CH2NH2）2.5[Mo0.5^（V）W0.5^（VI）O2（OC6H4O）2] 顺式二氧金属配合物 钼（V）配合物 钨（VI）配合物 1 2-二羟基苯 |
Synthesis,Crystal Structure,UV-vis and EPR Studies of (NH_3CH_2CH_2NH_2)_(2.5)[Mo_(0.5)~(V)W_(0.5)~(VI)O_2(OC_6H_4O)_2] |
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| LU,Xiao-Ming,a,b SONG,Fu-Gen a LOU,Fu-Yan a MAO,Xi-An b YE,Zhao-Hui b LU,Jing-Fen c a. Synthesis,Crystal Structure,UV-vis and EPR Studies of (NH_3CH_2CH_2NH_2)_(2.5)[Mo_(0.5)~(V)W_(0.5)~(VI)O_2(OC_6H_4O)_2][J]. Chinese Journal of Chemistry, 2003, 21(11): 1474-1477. DOI: 10.1002/cjoc.20030211116 |
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| Authors: | LU Xiao-Ming a b SONG Fu-Gen a LOU Fu-Yan a MAO Xi-An b YE Zhao-Hui b LU Jing-Fen c a |
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| Affiliation: | LU,Xiao-Ming,a,b SONG,Fu-Gen a LOU,Fu-Yan a MAO,Xi-An b YE,Zhao-Hui b LU,Jing-Fen c a Department of Chemistry,Capital Normal University,Beijing 100037,China b Wuhan Institute of Physics and Mathematics,Chinese Academy of Sciences,Wuhan,Hubei 430071,China cState Key Laboratory of Natural and Biomimetic Drugs,Medicine Science Center,Peking University,Beijing 100083,China |
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| Abstract: | Cis-dioxo-metal complex (NH_3CH_2CH_2NH_2)_ 2.5 [Mo (V) _ 0.5 W (VI) _ 0.5 O_2-(OC_6H_4O)_2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1,2-dihydroxybenzene in the mixed solvent of CH_3OH,CH_3CN and ethylenediamine,and characterized by X-ray diffraction,UV-vis and EPR analysis. Compared with its analogous complexes (NH_3CH_2CH_2~ NH_2)_3[Mo (V) O_2(OC_6H_4O)_2] 2 and (NH_3CH_2CH_2NH_2)_2[W (VI) -O_2(OC_6H_4O)_2] 3,the results show that tungsten(VI) is less active in redox than molybdenum(VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in [MO_2-(OC_6H_4O)_2] n - does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis -dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes. It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme,suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. |
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| Keywords: | cis -dioxo-molybdo(V)tungsten(VI) complex 1 2-dihydroxybenzene EPR UV-vis octahedral coordination |
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