Mechanistic evaluation of metal-catalyzed hydrogen-transfer processes: The Shvo catalyst as an example of computational unravelling

Aleix Comas-Vives*, Gregori Ujaque, Agustí Lledós

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

40 Citations (Scopus)

Abstract

Hydrogen-transfer processes allow hydrogenation under mild conditions reaching high selectivity. They use readily available solvents such as 2-propanol instead of molecular H2. The mechanism of these processes can be classified into: (a) Direct hydrogen-transfer or Meerwein-Ponndorf-Verley (MPV) reduction and (b) Hydridic route, with the formation of a metal-hydride species. The latter can be divided into both dihydridic and hydridic routes depending on the catalytic species involved, a dihydride or a monohydride, respectively. Within the monohydridic route the reaction can go through an inner-sphere mechanism (with substrate coordination) or through an outer-sphere mechanism (without coordination to the metal substrate). The proposed mechanisms for the hydrogen-transfer processes catalyzed by several metal complexes within the literature are reviewed, paying special attention to its computational analysis concerning the factors affecting the mechanism such as ligand lability and alkoxide stability. Afterwards, we focus on one of the most paradigmatic hydrogen-transfer processes catalyzed by the Shvo complex. It presents great versatility applied in a broad range of hydrogen-transfer processes to polar (ketones, imines) and non-polar (alkene, alkynes) bonds, and even successfully heterogenized by a sol-gel process.

Original languageEnglish
Pages (from-to)123-132
Number of pages10
JournalJournal of Molecular Structure: THEOCHEM
Volume903
Issue number1-3
DOIs
Publication statusPublished - 15 Jun 2009

Keywords

  • Hydrogen-transfer processes
  • Mechanistic analysis
  • Shvo catalyst
  • Theoretical calculations
  • Transition-metal complexes

Fingerprint

Dive into the research topics of 'Mechanistic evaluation of metal-catalyzed hydrogen-transfer processes: The Shvo catalyst as an example of computational unravelling'. Together they form a unique fingerprint.

Cite this