钴(Ⅱ)-氨基酸配合物催化性能与氧合性能的关系

doi:10.7503/cjcu20150578

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (2): 354.doi: 10.7503/cjcu20150578

钴(Ⅱ)-氨基酸配合物催化性能与氧合性能的关系

魏雅娜¹, 张新村², 李辉¹, 徐骞¹, 岳凡¹, 王吉德¹()

1. 新疆大学化学与化工学院, 石油天然气精细化工教育部和自治区共建重点实验室, 乌鲁木齐 830046
2. 新疆建筑材料设计研究院, 乌鲁木齐 830046

收稿日期:2015-07-22 出版日期:2016-02-10 发布日期:2016-01-13
作者简介:联系人简介: 王吉德, 男, 博士, 教授, 主要从事配位化学和催化研究. E-mail:awangjd@sina.cn
基金资助:
国家自然科学基金(批准号: 21162027, 21261022)资助

Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes^†

WEI Yana¹, ZHANG Xincun², LI Hui¹, XU Qian¹, YUE Fan¹, WANG Jide^1,^*()

1. Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region,Chemistry and Chemical Engineering of Xinjiang University, Urumqi 830046, China
2. Xinjiang Design Institute of Building Materials, Urumqi 830046, China

Received:2015-07-22 Online:2016-02-10 Published:2016-01-13
Contact: WANG Jide E-mail:awangjd@sina.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21162027, 21261022)

摘要/Abstract

摘要：

研究了13种钴(Ⅱ)-氨基酸配合物的可逆氧合性能和催化性能之间的关系, 通过配合物活化分子氧(O₂)氧化环己烯考察其催化性能. 结果表明, 13种钴(Ⅱ)-氨基酸配合物均具有不同程度的可逆氧合性能和催化活性. 配合物完成一个可逆吸氧周期的用时越短, 其可逆氧合性能越好, 催化性能越差; 相反, 吸氧周期长及可逆氧合性能差的配合物其催化性能却更好. 另外, 在对配合物不同配比的研究中发现, Co(Ⅱ)与氨基酸的摩尔比为1:3(或1:2)饱和配位时, 可逆吸氧性能较好, 但其催化性能较差, 环己烯转化率较低; 在1:1型配位不饱和时, 吸氧的可逆性较差, 但催化性能优良, 环己烯的转化率可达82.5%. 结合结构分析和理论计算的结果可知, 不同钴(Ⅱ)-氨基酸配合物的氧合可逆性和催化性能的差异, 主要归因于氨基酸配体的残基与Co(Ⅱ)的结合能力的不同. 氨基酸配体的残基与Co(Ⅱ)的结合能力越好, 越有利于配合物由高自旋态向低自旋态转化, 并与O₂可逆结合, 不利于烯烃基的取代, 配合物表现出较差的催化性能, 反之亦然.

关键词: 钴(Ⅱ)配合物, 氨基酸, 氧合反应, 环己烯, 催化性能

Abstract:

The relationship between oxygenation properties and corresponding catalytic performance of 13 natural amino acid-cobalt(Ⅱ) complexes were identified. The results indicate that for those complexes with reversible oxygenation properties, the shorter the time spent for completing a reversible oxygenation cycle is, the better their reversible oxygenation and the worse the property of their catalysis are. As a contrast, longer cycle time for completing a reversible oxygenation cycle attest to worse performance of reversible oxygenation but better property of catalysis. In particular, the results of glutamic cobalt(Ⅱ) complexes confirms that when the ratio of Co(Ⅱ) and ligand is 1:3, the reversible oxygenation property is good, while the catalytic reaction yields a low conversion rate of cyclohexene. On the other hand, the complex with Co(Ⅱ):ligand 1:1 led to a high conversion rate of cyclohexene. With the help of the preliminary structural study and theoretical calculation, we suppose that the difference between reversible oxygenation property and catalytic property are mainly due to the coordinating ability of amino acid ligands. The strong coordinating ability of amino acid ligands is favorably to the high spin to low spin transform for reversibly absorbing O₂. While the less favorably for vinyl replacement exhibited poor catalytic properties, and vice versa.

Key words: Cobalt(Ⅱ) complex, Amino acid, Oxygenation, Cyclohexene, Catalytic property

中图分类号:

O643
O657.6

TrendMD:

魏雅娜, 张新村, 李辉, 徐骞, 岳凡, 王吉德. 钴(Ⅱ)-氨基酸配合物催化性能与氧合性能的关系. 高等学校化学学报, 2016, 37(2): 354.

WEI Yana, ZHANG Xincun, LI Hui, XU Qian, YUE Fan, WANG Jide. Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes^†. Chem. J. Chinese Universities, 2016, 37(2): 354.

图/表 7

Fig.1 UV-Vis spectra of Co(Ⅱ)-His(A) and Co(Ⅱ)-Glu(B) complexes a. His or Glu; b. Co(Ⅱ); c. Co(Ⅱ)-His or Co(Ⅱ)-Glu in N2; d: Co(Ⅱ)-His or Co(Ⅱ)-Glu in O2.cL=1.0×10-3 mol/L, L=His, Glu; cCo=5.0×10-4 mol/L.

Fig.2 Reversible oxygenation property and dynamics results of Co(Ⅱ)-His(A) and Co(Ⅱ)-Glu(B) complexes The insets of (A) and (B) show the first cycle of oxygenation and deoxygenation of the complexes.

Fig.3 Relationship between catalytic performance and oxygenation property of amino acid cobalt(Ⅱ) complexes

Fig.4 Effect of composition of catalysts on the oxidation conversion of cyclohexene Reaction conditions: solvent-free, amount of cyclohexene: 1 mL,reaction temperature: 70 ℃, reaction time: 24 h.

Fig.5 Formation of the solid-state Co(Ⅱ)-Glu complexes characterized by UV-Vis a. Glu; b. Co(Ⅱ); c. Co-Glu in N2; d. Co-Glu in O2.

Fig.6 XRD patterns of glutamate cobalt(Ⅱ) complexes a. Simulated pattern; b. synthesized complexes.

Fig.7 Theoretical structural evolution of activating dioxygen by the Co(Ⅱ)-Glu complex with coordinating of ethylene

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钴(Ⅱ)-氨基酸配合物催化性能与氧合性能的关系

Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes^†

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钴(Ⅱ)-氨基酸配合物催化性能与氧合性能的关系

Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes†

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Relationship Between Reversible Oxygenation and Catalytic Properties of Amino Acid Cobalt Complexes^†