| 取代环戊二烯锆、铪络合物光解活泼自由基的ESR研究 |
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| 引用本文： | 纪海星,徐广智,陈寿山,刘以寅. 取代环戊二烯锆、铪络合物光解活泼自由基的ESR研究[J]. 波谱学杂志, 1987, 4(1): 53-60 |
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| 作者姓名： | 纪海星 徐广智 陈寿山 刘以寅 |
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| 作者单位： | 1. 中国科学院化学研究所 北京;2. 南开大学元素有机化学研究所 天津 |
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| 基金项目： | 国家自然科学基金会资助 |
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| 摘 要： | 本文用自旋捕捉术技与ESR相结合的方法,研究取代环成二烯锆、铪络物(RC5H4)2ZrCl2(R=H,CH3,C3H7,C4H9,C5H11,C6H11)及(RC5H4)2HfCl2(R=CH3,C2H5,C3H7)光解的活泼自由基。结果表明,取代环成二烯锆、铪络合物与取代环戊二烯钛结合物光解机理相同,即光解初级过程是M-(RC5H4)(M=Ti,Zr,Hf)π键的均裂。其差别在于RCpMCl2(M=Zr,Hf)可为PBN及ND捕获,并后者的加合物表现出氯核的分裂。
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| 关 键 词： | 自旋捕捉技术 锆络合物 自由基 ESR |
| 收稿时间： | 1986-09-12 |
ESR STUDY OF ACTIVE RADICALS PRODUCED BY PHOTOLYSIS OF SUBSTITUTED ZIRCONOCENE AND HAFNOCENE DICHLORIDE COMPLEX COMPOUNDS |
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| Ji Haixing and Xu Guangzhi. ESR STUDY OF ACTIVE RADICALS PRODUCED BY PHOTOLYSIS OF SUBSTITUTED ZIRCONOCENE AND HAFNOCENE DICHLORIDE COMPLEX COMPOUNDS[J]. Chinese Journal of Magnetic Resonance, 1987, 4(1): 53-60 |
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| Authors: | Ji Haixing and Xu Guangzhi |
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| Affiliation: | 1. Institute of Chemistry, Academia Sinica, Beijing;2. Institute of Elementry Organic Chemistry, Nankai University, Tianjin, China |
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| Abstract: | Active radicals produced by photolysis of substituted zirconocene dichloride complexes (RC5H4)2ZrCl2(R=H,CH3,C3H7,C4H9,C5,H11,C6H11) and hafnocene dichloride complexes(RC5H4)2HfCl2(R=CH3,C2H5, C3H7)were studied by combining spin trapping technique with ESR spectroscopy.The results show that the photolytic mechanisms of substituted zirconocene and hafnocene dichloride complexes are the same as those of titanocene dichloride complexes. In other words the primary process of photolysis is homolytic cleavage of the M-(RC5H4) (M=Ti, Zr, Hf)π bond. Only in the former case the free radicals RCpMCl2(M=Zr, Hf) can be trapped by PBN and ND. |
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| Keywords: | Spin trapping technique Zirconocene Complex ESR. |
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