Principle of Highly Selective Catalytic Reactions Proceeding through Metal-Olefin Complexes

金属-烯烃配合物高选择性催化反应原理

• 批准号: 62550630
• 负责人: KUROSAWA Hideo
• 金额: $ 1.22万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550630/
• 关键词: Olefin-metal complex; Homogeneous catalysis; 還元的脱離; 金属錯体触媒反応

The objective of this research project is to gain the better understanding, on the molecular level, of the highly selective catalytic reactions proceeding through metal-olefin complexes. Two primary results obtained during this research include: 1) The selectivity in the reductive elimination of -allyl(alkyl)metal complexes, which involves -olefinmetal complexes as a key intermediate, is controlled by the nature of metal (Ni)>Pd Pt) and the ancillary ligand (diphosphine monophosphine). 2) The selectivity in the transformation of the olefinmetal complexes depend on the nature of the olefin-metal bonding scheme; namely, the transformation of the -allyl(alkyl)(olefin)palladium to the C-C coupling product is enhanced by the more electron-withdrawing olefin ligand, and the transformation of the -allyl(olefin)platinum to a hydrido-platinum intermediate, a key to the catalytic olefin isomerization, is enhanced by the higher degree of olefin to metal electron donation.

本研究项目的目的是在分子水平上更好地了解通过金属-烯烃络合物进行的高选择性催化反应。研究结果表明：（1）以-烯烃金属配合物为关键中间体的-烯丙基（烷基）金属配合物的还原消除反应的选择性受金属（Ni）、Pd（Pt）和辅助配体（双膦单膦）的性质控制; 2)烯烃金属络合物转化的选择性取决于烯烃-金属键合方案的性质;即，-烯丙基（烷基）（烯烃）钯向C-C偶合产物的转化被更多吸电子的烯烃配体增强，并且-烯丙基（烯烃）铂向双-铂中间体的转化，这是催化烯烃异构化的关键，通过较高程度的烯烃对金属的电子给予而增强。

项目成果

Hideo Kurosawa: "Molecular Basis of Catalysis Involving Olefin and ^2-Allyl Complexes of Group 10 Metals" J. Synthetic Org. Chem. Japan. 46. 356-364 (1988)

Hideo Kurosawa：“涉及第 10 族金属的烯烃和 ^2-烯丙基配合物的催化作用的分子基础”J. Synthetic Org。

Hideo Kurosawa; Koichiro Ishii; Yoshikane Kawasaki; Shinji Murai: "NMR and Kinetic Studies on Phosphine-Induced Coupling of ^3-Methallyl-(acetylacetonato)palladium and -platinum: Uniquely Facile C-C Bond Formation with ^3-Allyl platinum Complex" Organomet

黑泽秀夫；

Hideo Kurosawa,;Hiroaki Ohnishi,;Mitsuhiro Emoto,;Yoshikane Kawasaki,;Shinji Murai: J.Am.Chem.Soc.110. 6272-6273 (1988)

Hideo Kurosawa,;Hiroaki Ohnishi,;Mitsuhiro Emoto,;Yoshikane Kawasaki,;Shinji Murai：J.Am.Chem.Soc.110。