Savkov, Boris Y. and Virovets, Alexander V. and Peresypkina, Eugenia V. and Potemkin, Vladimir A. and Palko, Nadezhda N. and Maksakov, Vladimir A. (2021) Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2021 (10). pp. 989-996. ISSN 1434-1948, 1099-0682
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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 similar to 25 degrees C have been studied. Two main types of products are formed in all studied reactions. One product is carbene cluster [Os-3(mu-H)(mu-Cl){eta(1)-C(CH3)N(CH2CH2)(2)X}(CO)(9)] (X=O, S, CH2) (3, 3 a and 3 b). Second product is cluster containing enamine ligand [Os-3(mu-H){mu-CH=CHN(C2CH2)(2)X)}(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 gamma-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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | OSMIUM CARBONYL HYDRIDES; MOLECULAR-GEOMETRY; STABLE ROTAMERS; COMPLEXES; DECACARBONYL; Carbene clusters; Stereochemistry; Stable rotamers; Conformational analysis; Heterocyclic amines activation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 20 Sep 2022 07:01 |
| Last Modified: | 20 Sep 2022 07:01 |
| URI: | https://pred.uni-regensburg.de/id/eprint/47604 |
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