Coordination preferences of 4-dimethylaminobut-3-en-2-one in thermally and photochemically activated reactions with Ru3(CO)12

Osintseva, S.V.; Shtel’tser, N.A.; Peregudov, A.S.; Kreindlin, A.Z.; Dolgushin, F.M.

Авторы: Osintseva Svetlana V., Shtel’tser Nikolay A., Peregudov Alexander S., Kreindlin Arkadii Z., Dolgushin Fedor M.
Журнал: Polyhedron
Том: 148
Год издания: 2018
Издательство: Pergamon Press
Местоположение издательства: United States
Первая страница: 147
Последняя страница: 160
DOI: 10.1016/j.poly.2018.04.007
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.
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Coordination preferences of 4-dimethylaminobut-3-en-2-one in thermally and photochemically activated reactions with Ru3(CO)12статья

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