Research output: Contribution to journal › Article › peer-review
Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines. / Savkov, Boris Y.; Virovets, Alexander V.; Peresypkina, Eugenia V. et al.
In: European Journal of Inorganic Chemistry, Vol. 2021, No. 10, 12.03.2021, p. 989-996.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines
AU - Savkov, Boris Y.
AU - Virovets, Alexander V.
AU - Peresypkina, Eugenia V.
AU - Potemkin, Vladimir A.
AU - Palko, Nadezhda N.
AU - Maksakov, Vladimir A.
N1 - Funding Information: The research was supported by the Ministry of Science and Education of the Russian Federation. Publisher Copyright: © 2021 Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/3/12
Y1 - 2021/3/12
N2 - 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.
AB - 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.
KW - Carbene clusters
KW - Conformational analysis
KW - Heterocyclic amines activation
KW - Stable rotamers
KW - Stereochemistry
UR - http://www.scopus.com/inward/record.url?scp=85099932104&partnerID=8YFLogxK
U2 - 10.1002/ejic.202001071
DO - 10.1002/ejic.202001071
M3 - Article
AN - SCOPUS:85099932104
VL - 2021
SP - 989
EP - 996
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 10
ER -
ID: 27639737