吡喃葡糖基氮杂环卡宾-钯(II)-吡啶配合物的NMR研究

doi:10.11938/cjmr20202806

波谱学杂志 ›› 2020, Vol. 37 ›› Issue (4): 505-514.doi: 10.11938/cjmr20202806

吡喃葡糖基氮杂环卡宾-钯(II)-吡啶配合物的NMR研究

周中高, 谢倩, 元洋洋, 李静, 路东亮, 陈正旺

赣南师范大学化学化工学院, 江西省高校功能材料化学重点实验室, 江西赣州 341000

收稿日期:2020-02-07 出版日期:2020-11-05 发布日期:2020-03-30
通讯作者: 周中高,Tel:0797-8393670,E-mail:zhgzhou@foxmail.com. E-mail:zhgzhou@foxmail.com
基金资助:
国家自然科学基金资助项目（21562002，21461002）；大学生创新创业训练计划项目（CX190009）；江西省学位与研究生教育教学改革研究项目（JXYJG-2017-135）；赣南师范大学研究生优质课程项目.

An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex

ZHOU Zhong-gao, XIE Qian, YUAN Yang-yang, LI Jing, LU Dong-liang, CHEN Zheng-wang

College of Chemistry and Chemical Engineering, Key Laboratory of Jiangxi University for Functional Materials Chemistry, Gannan Normal University, Ganzhou 341000, China

Received:2020-02-07 Online:2020-11-05 Published:2020-03-30

摘要/Abstract

摘要： 以溴化1-（2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖基）-3-丁基咪唑盐（化合物1）、吡啶和醋酸钯为原料，快速合成了空气稳定的1-（2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖基）-3-丁基-咪唑-2-亚基]-溴化钯（II）-吡啶（配合物2）.配合物2的结构中存在乙酰基-β-D-吡喃葡萄糖基，糖环上有多个手性碳，其核磁共振氢谱（¹H NMR）和碳谱（¹³C NMR）较复杂，不易归属.本文通过元素分析对配合物2的组成进行表征，运用1D和2D NMR技术（包括¹H NMR、¹³C NMR、DEPT135、DEPT90、DEPT45、COSY、¹H-¹³C HSQC、¹H-¹³C HMBC）对配合物2的¹H和¹³C NMR信号进行全归属.研究发现，在乙酰基-β-D-吡喃葡萄糖基的稠环上多个弱配位的氧和乙酰基氧原子上孤电子对的作用下，配合物2的氮杂环卡宾-钯（II）-吡啶金属键形成对稠环上碳氢化学环境的影响比对丁基的影响更为明显.

关键词: 液体核磁共振, 吡喃葡糖基氮杂环卡宾-钯(II)-吡啶

Abstract: A new air-stable and easy-to-handle 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-butyl-imidazol-2-ylidene] Pd(pyridine)Br₂ (complex 2) was synthesized from the imidazolium halide salts 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-butyl-midazolium bromide (compound 1) by reaction with Pd(OAc)₂ in pyridine. Complex 2 contains multiple chiral centers on the sugar ring. The molecular structures of complex 2 were determined with elemental analysis and liquid-state nuclear magnetic resonance (NMR) spectra. ¹H and ¹³C chemical shifts of complex 2 were fully assigned. It was found that the effects of the carbon and proton chemical environment on the sugar ring is more obvious than that on the butyl chain after formation of N-heterocyclic carbene-palladium(II)-pyridine (NHCs-Pd(II)-Py)-metal bond in the presence of multiple weakly coordinated oxygen.

Key words: liquid-state nuclear magnetic resonance, glucopyranosyl-based N-heterocyclic carbene-palladium(II)-pyridine

中图分类号:

O482.53

周中高, 谢倩, 元洋洋, 李静, 路东亮, 陈正旺. 吡喃葡糖基氮杂环卡宾-钯(II)-吡啶配合物的NMR研究[J]. 波谱学杂志, 2020, 37(4): 505-514.

ZHOU Zhong-gao, XIE Qian, YUAN Yang-yang, LI Jing, LU Dong-liang, CHEN Zheng-wang. An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex[J]. Chinese Journal of Magnetic Resonance, 2020, 37(4): 505-514.

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吡喃葡糖基氮杂环卡宾-钯(II)-吡啶配合物的NMR研究

An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex

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