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含有2,6-双（2,5-R-吡咯基）苯氧基（R =异丙基，苯基）配体且在失去乙烯过程中带有未取代金属环丁烷的钼和钨的单氧化吡咯亚胺烷基配合物。

Monoaryloxide Pyrrolide (MAP) Imido Alkylidene Complexes of Molybdenum and Tungsten That Contain 2,6-Bis(2,5-R-pyrrolyl)phenoxide (R = i-Pr, Ph) Ligands and an Unsubstituted Metallacyclobutane on Its Way to Losing Ethylene.

作者信息

Reithofer Michael R, Dobereiner Graham E, Schrock Richard R, Müller Peter

机构信息

Department of Chemistry, Massachusetts Institute of Technology 6-331 , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.

出版信息

Organometallics. 2013 May 13;32(9):2489-2492. doi: 10.1021/om400114h. Epub 2013 May 2.

DOI:10.1021/om400114h
PMID:23794779
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3688325/
Abstract

We report the synthesis of Mo and W MAP complexes that contain O-2,6-(2,5-R-pyrrolyl)CH (2,6-dipyrrolylphenoxide or ODPP) ligands in which R = i-Pr, Ph. W(NAr)(CH-t-Bu)(Pyr)(ODPP) (; Ar = 2,6-disopropylphenyl, Pyr = pyrrolide) reacts readily with ethylene to yield a metallacyclobutane complex, W(NAr)(CH)(Pyr)(ODPP) (). The structure of in the solid state shows that it is approximately a square pyramid with the WC ring spanning apical and basal positions. This SP' structure, which has never been observed as an actual intermediate, must now be regarded as an integral feature of the metathesis reaction.

摘要

我们报道了含有O-2,6-(2,5-R-吡咯基)CH（2,6-二吡咯基苯氧基或ODPP）配体（其中R = 异丙基、苯基）的钼和钨MAP配合物的合成。W(NAr)(CH-t-Bu)(Pyr)(ODPP)（；Ar = 2,6-二异丙基苯基，Pyr = 吡咯化物）与乙烯容易反应生成金属环丁烷配合物W(NAr)(CH)(Pyr)(ODPP)（）。固态下的结构表明它近似为一个方锥，其中WC环跨越顶端和基部位置。这种SP'结构，从未作为实际中间体被观察到，现在必须被视为复分解反应的一个整体特征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/8e8e37742472/om-2013-00114h_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/a5ad87942972/om-2013-00114h_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/a91d0cf8cb31/om-2013-00114h_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/9d528afea19e/om-2013-00114h_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/0eceab50880c/om-2013-00114h_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/8e8e37742472/om-2013-00114h_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/a5ad87942972/om-2013-00114h_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/a91d0cf8cb31/om-2013-00114h_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/9d528afea19e/om-2013-00114h_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/0eceab50880c/om-2013-00114h_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2dde/3688325/8e8e37742472/om-2013-00114h_0006.jpg

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