Abstract
Organometallic and bioinorganic chemical reactions involve transition metal complexes, which often possess several unpaired electrons on the metal center, giving rise to closely lying spin states, which may participate in reactivity. This chapter focuses on describing these concepts, and on showing that unpaired electrons and multi-state situations have a profound impact on chemical reactivity. It first provides suggestions for experimental probes of spin-state selectivity, and two-state reactivity (TSR) and multi-state reactivity (MSR) prospects. Next, the chapter presents theoretical exchange-enhanced reactivity (EER) concept that explains the underpinnings of spin selective reactivity. It introduces exchange interactions and their impact on H-abstraction, then applies the EER rule to the quintet and triplet states of FeIVO species to explain the origin of spin selective reactivity, and demonstrates its implications and manifestations of the concept in a variety of systems. Finally, the chapter discusses the various ways to probe spin-state effects by theory and experiment.
Original language | English |
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Title of host publication | Spin States in Biochemistry and Inorganic Chemistry |
Subtitle of host publication | Influence on Structure and Reactivity |
Publisher | Wiley-Blackwell |
Pages | 131-156 |
Number of pages | 26 |
ISBN (Electronic) | 9781118898277 |
ISBN (Print) | 9781118898314 |
DOIs | |
State | Published - 24 Nov 2015 |
Bibliographical note
Publisher Copyright:© 2016 John Wiley & Sons, Ltd. All rights reserved.
Keywords
- Bioinorganic chemistry
- Exchange-enhanced reactivity
- Multi-state reactivity
- Spin-states reactivity
- Transition metal complexes
- Two-state reactivity