Pericyclic organometallic reactions. Cycloaddition reactions of (η4-cycloheptatriene)Ru(CO)3. Crystal structure of tricarbonyl[(2,3,4,9-η)-bicyclo[4.2.1]non-2-ene-4,9-diyl-7,7,8,8-tetracarbonitrile]ruthenium

Zeev Goldschmidt, Elisheva Genizi, Hugo E. Gottlieb, Dafna Hezroni-Langermann, Heinz Berke, H. William Bosch, Josef Takats

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Abstract

4-Cycloheptatriene)Ru(CO)3 reacts with tetracyanoethylene (TCNE), 4-phenyltriazoline-3,5-dione (PTAD) and (carbomethoxy)maleic anhydride (CMA) to give stable 3 + 2 σ,π-allylic adducts. The 3 + 2 adduct with TCNE equilibrates via a [4,4]-sigmahaptotropic rearrangement with the less stable 6 + 2 adduct, which decomposes under the reaction conditions to the demetallated 6 + 2 adduct. It is concluded that σ,π-allylic adducts are in general more stable than their isomeric η4-π counterparts. The structure of the 3 + 2 TCNE adduct was determined by a single-crystal X-ray diffraction study.

Original languageEnglish
Pages (from-to)419-429
Number of pages11
JournalJournal of Organometallic Chemistry
Volume420
Issue number3
DOIs
StatePublished - 10 Feb 1991

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