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题名: The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand
作者: Li, C;  Zhou, DH;  Yao, XQ;  Liu, XM;  Lu, SW;  Han, XW;  Bao, XH
关键词: cyclopropanation ;  molecular mechanics/dynamics ;  carbene
刊名: CHINESE JOURNAL OF INORGANIC CHEMISTRY
发表日期: 2001-07-15
卷: 17, 期:4, 页:507-512
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear
研究领域[WOS]: Chemistry
英文摘要: A novel ruthenium catalytic system with 1R, 2R-cyclohexyl-N2P2 as ligand for the asymmetric cyclopropanation of styrene was investigated. Abnormal trans: cis phenomenon was found when the catalytic system was pretreated with AgOTf (silver triflate). The trans: cis is near 1: 1, but the cis-products has a little advantage. The molecular mechanics/dynamics were used to study this phenomenon. The geometric energies of two approaching states, which resulting in trans- and cis-products were compared. The results reveal that the energy of valence terms is not the major factor to decide the trans: cis ratio of cyclopropanation products because the difference on the energy of valence terms is very little (about 0.2kcal (.) mol(-1)), The theoretical calculation by molecular mechanics was in agreement to this result. But as for energy of nonbonding terms, the interaction of Van der waals between intermediate M1 and styrene to give the cis-products is so strong ( - 0.73 kcal (.) mol(-1)) that it offsets the disadvantage caused by elcetrostatic energy. So the total energy of interaction between M1 and styrene is favorable to give cis-products. But the difference of total energy for interaction of M1 and styrene to give trans- and cis-products is small. It is about 2,5kcal (.) mol(-1) This ensures the trans: cis ratio of cyclopropanation products is near 1: I, which is consistent with experimental results and decided by stereochemistry of N, P-ligand.
关键词[WOS]: COMPLEXES ;  LIGANDS
语种: 英语
WOS记录号: WOS:000169723100008
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/138964
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
2.Liaoning Normal Univ, Dept Chem, Dalian 116029, Peoples R China

Recommended Citation:
Li, C,Zhou, DH,Yao, XQ,et al. The exploration of novel ruthenium catalytic system for cyclopropanation (II) - Preliminary investigation on selectivity of trans: Cis controlled by stereochemistry of N,P-ligand[J]. CHINESE JOURNAL OF INORGANIC CHEMISTRY,2001,17(4):507-512.
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