Stereochemistry of the Thermal Rearrangement through Intramolecular Metathesis of Si−Si and Fe−Fe Bonds:  First Evidence for a Nonconcerted Mechanism

meso and rac isomers of (η5:η5-C5H4RMeSiSiMeRC5H4)Fe2(CO)2(μ-CO)2 (R = Ph, n-Bu) were synthesized and successfully separated for the first time. They were found to undergo the title rearrangement reaction in a nonstereospecific fashion, to give the products [RMeSi-η5-C5H4Fe(CO)2]2 as mixtures of mes...

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Bibliographic Details
Published in:Organometallics 2006-01, Vol.25 (1), p.133-139
Main Authors: Sun, Huailin, Pan, Yanbin, Huang, Xuebin, Guo, Zhonghuai, Zhang, Zhensheng, Zhang, Huili, Li, Jinmeng, Wang, Fei
Format: Article
Language:English
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Summary:meso and rac isomers of (η5:η5-C5H4RMeSiSiMeRC5H4)Fe2(CO)2(μ-CO)2 (R = Ph, n-Bu) were synthesized and successfully separated for the first time. They were found to undergo the title rearrangement reaction in a nonstereospecific fashion, to give the products [RMeSi-η5-C5H4Fe(CO)2]2 as mixtures of meso and rac isomers in ratios of about 1:1. This is direct evidence to rule out the concerted free radical mechanism that is currently used to explain this reaction. A new mechanism involving activation of the Si−Si bond by a coordinatively unsaturated iron center is suggested.
ISSN:0276-7333
1520-6041
DOI:10.1021/om050622z