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[Ru（η^5-C9H7）{κ^3（P，C，C）-PPh2（CH2CHCH2）}（PPh3）][PF6]异构化机制理论研究 被引量：1

Theoretical Study on the Isomerization of [Ru（η^5-C9 H7 ） { κ^3 （ P, C, C）-PPh2 （CH2 CHCH2 ） } （ PPh3 ） ] [PF6 ]
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摘要 采用密度泛函理论(DFT)中的B3LYP方法,在6-31g**基组水平上研究了配合物[Ru(η5-C9H7){κ3(P,C,C)-PPh2(CH2CHCH2)}(PPh3)][PF6]的模型化合物[Ru(η5-C9H7){κ3(P,C,C)-PH2(CH2CHCH2)}(PH3)][PF6]的两个异构体1和2的相互转化机制.计算结果表明,从1到2活化能为11.81kcal/mol,1比2稳定,两者之间的能量差为4.63 kcal/mol.根据分子轨道对称性剖析了它们的相对稳定性.研究表明,异构体1比2稳定是由于1中的碳碳双键和金属之间能形成有效的反馈π键,增强了金属和碳碳双键之间的作用,而2中难以形成有效的反馈π键. The isomerization of [Ru （ η^5 -C9 H7 ） （ κ^3 （ P, C, C）-PPH2 （CH2 CH CH2 ） } （ PH3 ） ][PF6 ] which is the model of [Ru （η^5-C9 H7 ） { κ^3 （P, C, C）-PPh2 （CH2 CHCH2 ） } （PPh3）-] [PF6 ] is investigated theoretically using the Becke3LYP （B3LYP） theory at the basis set 6-31g·· level. The activation energy for the isomer- ization is calculated to be 11.81 kcal/mol. The results indicate that isomer 1 is more stable than 2 by -4.63 kcal/mol. Their relative stability is analyzed in terms of molecular orbital symmetry, and it is found more effective back-donation from the metal center to the antibonding orbital of C= C bond in 1, leading to its higher stability.
作者 赵义 王宾 朱秀芳 毕思玮
机构地区 曲阜师范大学化学科学学院
出处 《曲阜师范大学学报（自然科学版）》 CAS 2006年第2期76-80,共5页 Journal of Qufu Normal University(Natural Science)
基金 国家自然科学基金资助项目(20473047)
关键词 半安定性 杂化的烯丙基磷配体 密度泛函方法 前线轨道 反馈π键 hemilability hybrid phosphine-olefin ligands density functional theory （DFT） frontier orbital back-donation
分类号 O627 [理学—有机化学]
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参考文献16

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同被引文献12

  • 1丁养军,张振伟,朱树芬,毕思玮.CpRu(PPh_3)_2SSi^iPr_3与SCNR(R=Ph,1-Naphthyl)反应的结构、成键与机理的理论研究[J].化学学报,2007,65(10):943-949. 被引量：4
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曲阜师范大学学报（自然科学版）
2006年 第2期

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