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

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Title: 3d/4f Coordination Clusters as Cooperative Catalysts for Highly Diastereoselective Michael Addition Reactions
Author(s): Griffiths, K
Tsipis, AC
Kumar, P
Townrow, OPE
Abdul-Sada, A
Akien, GR
Baldansuren, A
Spivey, AC
Kostakis, GE
Item Type: Journal Article
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.
Publication Date: 7-Aug-2017
Date of Acceptance: 1-Aug-2017
URI: http://hdl.handle.net/10044/1/52121
DOI: https://dx.doi.org/10.1021/acs.inorgchem.7b01011
ISSN: 0020-1669
Publisher: American Chemical Society
Start Page: 9563
End Page: 9573
Journal / Book Title: INORGANIC CHEMISTRY
Volume: 56
Issue: 16
Copyright Statement: © 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry , after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.inorgchem.7b01011
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
DENSITY-FUNCTIONAL-APPROACH
FRIEDEL-CRAFTS ALKYLATION
FRONTIER-ELECTRON THEORY
SCHIFF-BASE COMPLEX
BARBITURIC-ACID
CHEMICAL-REACTIVITY
BIMETALLIC CATALYSIS
NITROALDOL REACTIONS
WATER OXIDATION
TAUTOMERISM
0302 Inorganic Chemistry
0904 Chemical Engineering
0399 Other Chemical Sciences
Inorganic & Nuclear Chemistry
Publication Status: Published
Embargo Date: 2018-08-07
Appears in Collections:Chemistry
Faculty of Natural Sciences



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