Griffiths, Kieran, Tsipis, Athanassios C, Kumar, Prashant, Townrow, Oliver P E, Abdul-Sada, Alaa, Akien, Geoffrey R, Baldansuren, Amgalanbaatar, Spivey, Alan C and Kostakis, George E (2017) 3d/4f Coordination clusters as cooperative catalysts for highly diastereoselective Michael addition reactions. Inorganic Chemistry, 56 (16). pp. 9563-9573. ISSN 0020-1669
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Abstract
Michael addition (MA) is one of the most well studied chemical transformation in synthetic chemistry. Here, we re-port the synthesis and crystal structures of a library of 3d/4f coordination clusters (CCs) formulated as ZnII2YIII2L4(solv)X(Z)Y and study their catalytic properties towards the MA of nitrostyrenes with barbituric acid deriva-tives. Each CC presents two borderline hard/soft Lewis acidic ZnII centers and two hard Lewis acidic YIII centers in a defect dicubane topology that brings the two different metals into a proximity of {\~{}}3.3 {\AA}. DFT computational studies suggest that these tetrametallic CCs dissociate in solution to give two catalytically active dimers, each containing one 3d and one 4f metal which act cooperatively. The mechanism of catalysis has been corroborated via NMR, EPR and UV-Vis. The present work demonstrates for the first time the successful use of 3d/4f CCs as efficient and high diastereose-lective catalysts in MA reactions.
Item Type: | Article |
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Schools and Departments: | School of Life Sciences > Chemistry |
Subjects: | Q Science > QD Chemistry > QD0146 Inorganic chemistry |
Depositing User: | Georgios Kostakis |
Date Deposited: | 24 Jul 2017 16:39 |
Last Modified: | 02 Jul 2019 15:02 |
URI: | http://sro.sussex.ac.uk/id/eprint/69426 |
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📧 Request an updateProject Name | Sussex Project Number | Funder | Funder Ref |
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Defect dicubane 3d/Dy(III) Coordination Clusters: Heading for materials displaying catalytic properties | G1632 | EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL | EP/M023834/1 |