Journal
CHEMICAL REVIEWS
Volume 119, Issue 14, Pages 8231-8261Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemrev.8b00561
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Funding
- Deutsche Forschungsgemeinschaft
- European Research Council (ERC) under the European Union Horizon 2020 Research and Innovation Program [669054]
- Alexander von Humboldt Foundation
- NSERC
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The study of main-group molecules that behave and react similarly to transition-metal (TM) complexes has attracted significant interest in recent decades. Most notably, the attractive idea of replacing the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main group elements, however, lack the electronic flexibility of TM complexes that arises from combinations of empty and filled d orbitals and that seem ideally suited to bind and activate many substrates. In this review, we look at boron, an element that despite its nonmetal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in interelement cooperative systems, diboron molecules, and hypovalent complexes the fifth element can acquire a truly metallomimetic character. As we discuss, this character is powerfully demonstrated by the reactivity of boron-based molecules with H-2, CO, alkynes, alkenes and even with N-2.
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