高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (6): 914.

• 论文 • 上一篇    下一篇

高分辨NMR研究金属盐对水溶性铑膦配合物分子结构的影响

袁友珠, 张宇, 叶剑良, 廖新丽, 姚春香, 杨意泉, 蔡启瑞   

  1. 厦门大学化学系, 物理化学研究所, 固体表面物理化学国家重点实验室, 厦门 361005
  • 收稿日期:1998-10-21 出版日期:1999-06-24 发布日期:1999-06-24
  • 通讯作者: 袁友珠,男,36岁,博士,教授.
  • 作者简介:袁友珠,男,36岁,博士,教授.
  • 基金资助:

    国家自然科学基金(批准号:29873037);中国石油化学工业总公司联合资助“九五”重大项目资助

Influence of Metal Salt on Molecular Structure of Water-soluble Rhdium-phosphine Complex

YUAN You-Zhu, ZHANG Yu, YE Jian-Liang, LIAO Xin-Li, YAO Chun-Xiang, YANG Yiquan, TSAI Khi-Rui   

  1. Department of Chemistry, Institute of Physical Chemistry, State Key Laboratory for Physical Chemistry of the Solid Surface, Xiamen University, Xiamen, 361005
  • Received:1998-10-21 Online:1999-06-24 Published:1999-06-24

摘要: 用高分辨NMR研究了NaCl、NiSO4、CuSO4、Fe2(SO4)3和Cr2(SO4)3对水溶性铑膦配合物HRh(CO)(TPPTS)3[TPPTS;P(m-C6H4SO3Na)3]分子结构的影响.31P(1H)和1HNMR谱显示,于室温下在HRh(CO)(TPPTS)3中加入的NaCl或NiSO4对配合物的特征31P(1H)和1HNMR谱峰无明显影响;当加入CuSO4后,配合物的Rh-H质子峰强度弱化明显,进而消失,且原配合物的特征磷谱峰强度减弱,新生成的磷物种谱峰逐渐成为磷谱的主要物种.当加入Fe2(SO4)3或Cr2(SO4)3后,三价金属离子的强顺磁性使NMR灵敏度下降,谱峰宽化,该2种盐均易与水溶性铑膦配合物产生强烈的相互作用,易使配合物特征谱峰消失.实验结果表明,上述金属盐对配合物结构破坏性大小的顺序为;Fe2(SO4)3>Cr2(SO4)3>CuSO4》NiSO4~NaCl.

关键词: 31P(1H)NMR, 1HNMR, 水溶性铑膦配合物, 金属盐

Abstract: The molecular structure of water-soluble phosphine-rhdium complex HRh(CO)(TPPTS)3[TPPTS:P(m-C6H4SO3Na)3]affected by the metal salts, e.g., NaCl, NiSO4, CuSO4, Fe2(SO4)3and Cr2(SO4)3was investigated in connection with the biphasic catalysis system by means of high resolution liquid NMR. No evident change in the spectra of 31P(1H)NMR and 1HNMR of the watersoluble complex was observed by addition of NaCl and NiSO4.When CuSO4was added into the complex, however, the peak intensity of 1HNMR due to HRh diminished and accompanied with the gradual disappearance of the phosphorus species of the complex and the appearance of the newborn phosphorus species in the 31P(1H)NMR spectra. Moreover, the characteristic twin signals of the complex at δ=44.8, 43.6 in the 31P(1H)NMR were completely replaced by the new complexes at δ =28.0-33.4 when Fe2(SO4)3was added. The similar result was obtained in the case of Cr2(SO4)3, when higher concentration of Cr2(SO3)4was used. The results obtained shown that a decreasing order of influence of salt on the molecular structure of the complex is: Fe2(SO4)3>Cr2(SO3)4>CuSO4NiSO4~NaCl.

Key words: 31P(1H)NMR, 1HNMR, Water-soluble phosphine rhodium complex, Metal salt

中图分类号: 

TrendMD: