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3d/4f Coordination clusters as cooperative catalysts for highly diastereoselective Michael addition reactions

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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 Kostakis
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.

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 Chemistry

ISSN

0020-1669

Publisher

American Chemical Society

Issue

16

Volume

56

Page range

9563-9573

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2017-07-24

First Open Access (FOA) Date

2018-08-07

First Compliant Deposit (FCD) Date

2017-07-24

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