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3d/4f Coordination Clusters as Cooperative Catalysts for Highly Diastereoselective Michael Addition Reactions.

Authors
  • Griffiths, Kieran1
  • Tsipis, Athanassios C2
  • Kumar, Prashant1
  • Townrow, Oliver P E1
  • Abdul-Sada, Alaa1
  • Akien, Geoffrey R3
  • Baldansuren, Amgalanbaatar4
  • Spivey, Alan C5
  • Kostakis, George E1
  • 1 Department of Chemistry, School of Life Sciences, University of Sussex , Brighton BN1 9QJ, U.K.
  • 2 Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina , 451 10 Ioannina, Greece. , (Greece)
  • 3 Department of Chemistry, Lancaster University , Lancaster LA1 4YB, U.K.
  • 4 School of Chemistry, The University of Manchester , Manchester M13 9PL, U.K.
  • 5 Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, U.K.
Type
Published Article
Journal
Inorganic Chemistry
Publisher
American Chemical Society
Publication Date
Aug 21, 2017
Volume
56
Issue
16
Pages
9563–9573
Identifiers
DOI: 10.1021/acs.inorgchem.7b01011
PMID: 28783350
Source
Medline
License
Unknown

Abstract

Michael addition (MA) is one of the most well studied chemical transformation in synthetic chemistry. Here, we report 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 toward the MA of nitrostyrenes with barbituric acid derivatives. 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 Å. Density functional theory computational studies suggest that these tetrametallic CCs dissociate in solution to give two catalytically active dimers, each containing one 3d and one 4f metal that act cooperatively. The mechanism of catalysis has been corroborated via NMR, electron paramagnetic resonance, and UV-vis. The present work demonstrates for the first time the successful use of 3d/4f CCs as efficient and high diastereoselective catalysts in MA reactions.

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