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

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

Journal

European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682

Output data

Year: 2021, Volume: 2021, Number: 10, Pages: 989-996 Pages count : 8 DOI: 10.1002/ejic.202001071

Authors

Savkov Boris Y. ¹ , Virovets Alexander V. ² , Peresypkina Eugenia V. ² , Potemkin Vladimir A. ³ , Palko Nadezhda N. ⁴ , Maksakov Vladimir A. ^1,5

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences
2	University of Regensburg
3	South Ural State University
4	I.Ya. Postovsky Insititute of Organic Synthesis of the Ural Branch of the Russian Academy of Sciences
5	Novosibirsk State University

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.

Savkov B.Y. , Virovets A.V. , Peresypkina E.V. , Potemkin V.A. , Palko N.N. , Maksakov V.A.
Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines
European Journal of Inorganic Chemistry. 2021. V.2021. N10. P.989-996. DOI: 10.1002/ejic.202001071 WOS Scopus РИНЦ OpenAlex

Published print:

Jan 7, 2021

Web of science:	WOS:000611931800001
Scopus:	2-s2.0-85099932104
Elibrary:	44983686
OpenAlex:	W3120634529

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