Unusual outcome of the thermolytic condensation of diazoarylmethanes with a [tricarbonyl(畏⁶-2-p-tolyl)chromium]2-oxazolyl chelate of tetracarbonylrhenium

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• 作者：Christophe Werl茅 ; Xavier-Fr茅d茅ric Le Goff ; Jean-Pierre Djukic
• 关键词：Rhenium carbonyls ; Metallacycles ; Diazoalkanes ; Fischer carbenes
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：751
• 期：Complete
• 页码：754-759
• 全文大小：807 K

文摘

A new Cr(CO)₃-bound cyclorhenated 2-phenyl,2-oxazoline derivative was synthesized and treated with two different phenyldiazomethanes, namely Ph₂CN₂ and (t-Bu)(Ph)N₂ under thermolytic conditions in apolar solvents. With the former diazomethane the reaction affords mainly a new bimetallic electron-saturated species resulting from the insertion of the Ph₂C moiety into the C_Ar-Re bond of the rhenacyclic substrate. With the latter diazomethane substituted with one t-butyl group, the reaction quite unexpectedly leads to a new Re(CO)₄ metallacycle in which an ortho position is occupied by a (Ph)(t-Bu)(H)C-group, as a possible consequence of an unprecedented insertion-transposition of the Re-centred moiety by C-H bond activation. The results are supported by 6 X-ray structures and analytical informations.