Pericyclic organometallic reactions. Cycloaddition reactions of (η-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

(η⁴-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.