金属有机作业

Relative Reaction Rates of Olefin Substrates with Ruthenium(II) CarbeneMetathesis Initiators1 Michael Ulman and Robert H. Grubbs *

The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 Organometallics, 1998, 17 (12), pp 2484–2489

DOI: 10.1021/om9710172

Publication Date (Web): May 13, 1998

Abstract

The metathesis of terminal olefins having different steric bulk and different geometries as well as electronically different para-substituted styrenes was studied with the ruthenium-based metathesis initiators trans-(PCy3)2Cl2Ru CHR. Bulkier olefins were found to react slower, and trans internal olefins were found to be slower than cis. The kinetic product of all reactions was found to be the alkylidene rather than the methylidene. Observed effects were used to explain the mechanism of ring-opening cross metathesis. No linear electronic effects were observed.

相对反应速率的烯烃基板与钌(II)CarbeneMetathesis Initiators1

迈克尔·阿尔曼和罗伯特·h·拉布*

阿诺德和梅布尔贝克曼实验室的化学合成、化学和化学工程分工,加州理工学院,加州帕萨迪纳市,91125

有机金属化合物,1998,17(12),2484 - 2489页

DOI:10.1021 / om9710172

出版日期(Web):1998年5月13日

文摘

烯烃复分解的终端具有不同空间的体积和不同几何图形以及电子不同的对位取代了styrenes与钌建立复分解发起者反式-(PCy3)2 cl2ru对应。笨重的烯烃反应被发现得较慢,反式内部烯烃被发现是慢于cis。产品的所有反应的动力学被发现的而不是methylidene烷叉。观察到的结果被用来解释机制的开环交叉置换作用。没有线性电子效果观察。

Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes Donde R. Anderson †, Thay Ung ‡, Garik Mkrtumyan‡, Guy Bertrand #, Robert H. Grubbs *† and Yann Schrodi ‡

The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, Materia, Inc., 60 N. San Gabriel Boulevard, Pasadena, California 91107, and UCR-CNRS Joint Research Chemistry Laboratory, Department of Chemistry, University of California, Riverside, California 92521

Organometallics, 2008, 27 (4), pp 563–566

DOI: 10.1021/om7008028

Publication Date (Web): January 12, 2008

Abstract

The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes.

烯烃复分解催化剂轴承循环动力学选择性（烷基）（氨基）卡宾

·安德森†，，加里克克尔图米扬‡#，Guy贝特朗，罗伯特H. Grubbs *†和Yann schrodi‡

阿诺德和梅布尔贝克曼实验室化学合成，化学与生物化学工程，加州理工大学，帕萨迪纳，加利福尼亚91125，中药，Inc.，60国圣加布里埃尔大道，帕萨迪纳，加利福尼亚91107，和ucr-cnrs联合研究化学实验室，化学系，加利福尼亚大学，加利福尼亚河畔，92521

有机金属化合物，2008，27（4），页563–566

DOI：10.1021/om7008028