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3d/4f Coordination Clusters as Cooperative Catalysts for Highly Diastereoselective Michael Addition Reactions
File | Description | Size | Format | |
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3d_4f_MA_Final.docx | Accepted version | 2.09 MB | Microsoft Word | View/Open |
Title: | 3d/4f Coordination Clusters as Cooperative Catalysts for Highly Diastereoselective Michael Addition Reactions |
Authors: | 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. |
Issue 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 |
Appears in Collections: | Chemistry Faculty of Natural Sciences |