Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines

Boris Y. Savkov, Alexander V. Virovets, Eugenia V. Peresypkina, Vladimir A. Potemkin, Nadezhda N. Palko, Vladimir A. Maksakov

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование

Аннотация

Reactions of the [Os3H2(CO)10] cluster complex (1) with six-membered heterocyclic amines (morpholine, thiomorpholine, piperidine) and halohydrocarbons (CH2Cl2, ClHC=CHCl, CH2=CCl2) at ∼25 °C have been studied. Two main types of products are formed in all studied reactions. One product is carbene cluster [Os3(μ−H)(μ−Cl){η1−C(CH3)N(CH2CH2)2X}(CO)9] (X=O, S, CH2) (3, 3 a and 3 b). Second product is cluster containing enamine ligand [Os3(μ−H){μ-CH=CHN(C2CH2)2Х)}2(CO)10] (X=O, S, CH2) (2, 2 a and 2 b). The carbene ligand is assembled on a cluster, from three organic molecules, thus representing the first example of carbene ligands formed in this way. Clusters with carbene ligand exist as two stable isomers (rotamers hindered towards the Os−C bond), as confirmed by NMR studies and conformational analysis. We have found that in reactions of cluster 1 with acyclic amines containing an oxygen atom in γ-position (likely morpholine in CH2Cl2), only complexes with bridging enamine ligands are formed. Compounds 2 a, 2 b, 3 and 3 b are characterized by single-crystal X-ray diffraction.

Язык оригиналаанглийский
Страницы (с-по)989-996
Число страниц8
ЖурналEuropean Journal of Inorganic Chemistry
Том2021
Номер выпуска10
Ранняя дата в режиме онлайн7 янв 2021
DOI
СостояниеОпубликовано - 12 мар 2021

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