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New Insights into the Molecular Mechanism of H2 Activation

  • Guixiang Zeng
  • Yong Guo
  • Shuhua Li
Chapter
First Online:

Abstract

Mechanistic studies of H2 activation by the newly developed frustrated Lewis acid–Lewis base pairs, main-group metal complexes, transition-metal thiolate complexes, and transition-metal-based pincer ligand catalysts have been reviewed in this chapter. The reaction of H2 with frustrated Lewis acid–Lewis base pairs and main-group metal complexes is found to proceed via an unprecedented concerted Lewis acid–Lewis base mechanism. The molecular mechanism of H2 with transition metal thiolate complexes depends on the transition metals. The iridium thiolate complex splits the H–H bond through the oxidation addition step, while the rhodium thiolate complex heterolytically cleaves the H–H bond with a nonclassical dihydrogen complex as the intermediate. In the reaction of H2 with the transition-metal-based pincer ligand complex, the metal center and the pincer ligand work cooperatively through the dearomatization/aromatization process of the pincer ligand.

Keywords

Lewis Base Free Energy Barrier Heterolytic Cleavage Benzylic Carbon Thiolate Complex 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Notes

Acknowledgment

This work was supported by the National Natural Science Foundation of China (Grant Nos. 20625309 and 20833003)

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© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  1. 1.Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational ChemistryNanjing UniversityNanjingPeople’s Republic of China

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