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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Transition-Metal Hydride Radical Cations.

Yue Hu1, Anthony P Shaw2, Deven P Estes1

  • 1Department of Chemistry, Columbia University , New York, New York 10027, United States.

Chemical Reviews
|February 2, 2016
PubMed
Summary

Transition-metal hydride radical cations (TMHRCs) are crucial in chemical reactions. This review details their synthesis, stability, properties, and decomposition pathways based on experimental studies up to 2014.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Reaction Mechanisms

Background:

  • Transition-metal hydride radical cations (TMHRCs) are key intermediates in various chemical and biochemical processes.
  • Understanding TMHRCs is vital for explaining reactivity and developing new applications.
  • Their inherent sensitivity has historically limited their study and application.

Purpose of the Study:

  • To provide a comprehensive review of experimental studies on TMHRCs published through 2014.
  • To focus on isolated and observed TMHRC species.
  • To consolidate knowledge on TMHRC synthesis, stability, properties, decomposition, and reactivity.

Main Methods:

  • Survey of experimental methods for TMHRC generation and synthesis.
  • Analysis of reported data on TMHRC stability and fundamental properties, particularly the M-H bond.
  • Review of studies detailing TMHRC decomposition pathways and reactions.

Main Results:

  • Numerous TMHRCs have been synthesized, characterized, or identified as intermediates over the past four decades.
  • Key properties, stability, and decomposition routes of various TMHRCs have been experimentally investigated.
  • Reactions where TMHRCs act as intermediates have been documented.

Conclusions:

  • This review consolidates experimental findings on TMHRCs up to 2014.
  • It highlights advancements in understanding TMHRC synthesis, stability, and reactivity.
  • The findings provide a foundation for future research and applications of these important species.