3d_4f_MA_Final.pdf (1.72 MB)
3d/4f Coordination clusters as cooperative catalysts for highly diastereoselective Michael addition reactions
journal contribution
posted on 2023-06-09, 07:23 authored by Kieran Griffiths, Athanassios C Tsipis, Prashant Kumar, Oliver P E Townrow, Alaa Abdul-Sada, Geoffrey R Akien, Amgalanbaatar Baldansuren, Alan C Spivey, George KostakisGeorge KostakisMichael 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.
Funding
Defect dicubane 3d/Dy(III) Coordination Clusters: Heading for materials displaying catalytic properties; G1632; EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL; EP/M023834/1
History
Publication status
- Published
File Version
- Accepted version
Journal
Inorganic ChemistryISSN
0020-1669Publisher
American Chemical SocietyExternal DOI
Issue
16Volume
56Page range
9563-9573Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2017-07-24First Open Access (FOA) Date
2018-08-07First Compliant Deposit (FCD) Date
2017-07-24Usage metrics
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