在乙烯存在下，通过钼（IV）配合物将乙烯基三丁基锡催化同系化为烯丙基三丁基锡。

Catalytic homologation of vinyltributylstannane to allyltributylstannane by Mo(IV) complexes in the presence of ethylene.

作者信息

Schrock Richard R, Duval-Lungulescu M, Tsang W C Peter, Hoveyda Amir H

机构信息

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

出版信息

J Am Chem Soc. 2004 Feb 25;126(7):1948-9. doi: 10.1021/ja039173p.

DOI:10.1021/ja039173p

PMID:14971923

Abstract

We have found that CH2=CHSnBu3 is converted into CH2=CHCH2SnBu3 catalytically in the presence of Mo(IV) olefin complexes such as Mo(NAr)(CH2CH2)[biphen] (where Ar = 2,6-i-Pr2C6H3 and [biphen]2- = 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diolate). The proposed mechanism involves formation of a metalacyclopentane (MC4) complex from ethylene and CH2=CHSnBu3, "contraction" of this MC4 complex to a metalacyclobutane (MC3) complex, and finally metathesis of the MC3 complex to give CH2=CHCH2SnBu3 and Mo(NAr)(CH2)[biphen]. These new findings suggest (inter alia) that contraction of an MC4 ring to an MC3 ring may be a much more common mode of decomposition of metalacyclopentane rings in d0 complexes than previously believed.

摘要

我们发现，在诸如Mo(NAr)(CH2CH2)[biphen]（其中Ar = 2,6-二异丙基苯基且[biphen]2- = 3,3'-二叔丁基-5,5',6,6'-四甲基-1,1'-联苯-2,2'-二醇）的Mo(IV)烯烃配合物存在下，CH2=CHSnBu3可被催化转化为CH2=CHCH2SnBu3。提出的机理涉及由乙烯和CH2=CHSnBu3形成金属环戊烷（MC4）配合物，该MC4配合物“收缩”为金属环丁烷（MC3）配合物，最后MC3配合物发生复分解反应生成CH2=CHCH2SnBu3和Mo(NAr)(CH2)[biphen]。这些新发现（尤其）表明，在d0配合物中，MC4环收缩为MC3环可能是金属环戊烷环分解的一种比以前认为的更为常见的模式。