Coordination preferences of 4-dimethylaminobut-3-en-2-one in thermally and photochemically activated reactions with Ru3(CO)12статья
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Дата последнего поиска статьи во внешних источниках: 10 августа 2018 г.
Аннотация:The thermally and photochemically activated reactions of Ru3(CO)12 with 4-dimethylaminobut-3-en-2-one (L) were studied and several mononuclear and polynuclear products were isolated and fully characterized by a combination of spectroscopic IR and multinuclear NMR data as well by single-crystal X-ray diffraction studies. Chelate five-membered oxaruthenacycles found to be present in all the isolated organometallic products are formed via Cβ-H activation reactions. These metallacycles can be bound to other ruthenium atoms in the different modes, namely, through π-coordination to the olefinic bond, through σ-coordination to the Cα atom of the starting ligand, and by coordination through the lone pair of the oxygen atom. The coordination of a metal atom to the Cα atom caused by an isomerization of the ligand to form partially imine C=N bond and migration of the olefinic bond has not been observed previously in reactions of Ru3(CO)12 with oxadienes. The formation of the six-membered chelate azaoxaruthenacycles in the reaction with L is accompanied by a migration and reduction of the olefinic bond. These chelates are significantly less stable than the five-membered chelates and involved coordination to other metal atoms to form polynuclear products. The structural and spectroscopic features and possible transformations pathways of the resulting complexes are discussed.