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Open AccessReview

Base Catalysis by Mono- and Polyoxometalates

by 1,2,* and 1
Laboratory for Materials and Structures, Institute of Innovative Research, Tokyo Institute of Technology, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8503, Japan
Japan Science and Technology Agency (JST), Precursory Research for Embryonic Science and Technology (PRESTO), 4-1-8 Honcho, Kawaguchi 332-0012, Japan
Author to whom correspondence should be addressed.
Catalysts 2017, 7(11), 345;
Received: 17 October 2017 / Revised: 9 November 2017 / Accepted: 13 November 2017 / Published: 16 November 2017
(This article belongs to the Special Issue Recent Advances in Polyoxometalate-Catalyzed Reactions)
In sharp contrast with acid-, photo-, and oxidation-catalysis by polyoxometalates, base catalysis by polyoxometalates has scarcely been investigated. The use of polyoxometalates as base catalysts have very recently received much attention and has been extensively investigated. Numerous mono- and polyoxometalate base catalyst systems effective for the chemical fixation of CO2, cyanosilylation of carbonyl compounds, and C–C bond forming reactions have been developed. Mono- and polyoxometalate base catalysts are classified into four main groups with respect to their structures: (a) monomeric metalates; (b) isopolyoxometalates; (c) heteropolyoxometalates; and (d) transition-metal-substituted polyoxometalates. This review article focuses on the relationship among the molecular structures, the basic properties, and the unique base catalysis of polyoxometalates on the basis of groups (a)–(d). In addition, reaction mechanisms including the specific activation of substrates and/or reagents such as the abstraction of protons, nucleophilic action toward substrates, and bifunctional action in combination with metal catalysts are comprehensively summarized. View Full-Text
Keywords: polyoxometalate; base catalysis; chemical fixation of CO2; cyanosilylation; C–C bond forming reactions; bifunctional catalyst; charge density polyoxometalate; base catalysis; chemical fixation of CO2; cyanosilylation; C–C bond forming reactions; bifunctional catalyst; charge density
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Kamata, K.; Sugahara, K. Base Catalysis by Mono- and Polyoxometalates. Catalysts 2017, 7, 345.

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