Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO 2 and CO

Ekambaram Balaraman, Chidambaram Gunanathan, Jing Zhang, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

338 Citations (Scopus)

Abstract

Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO 2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO 2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate 'green' reactions. A possible mechanism involves metal-ligand cooperation by aromatization-dearomatization of the heteroaromatic pincer core.

Original languageEnglish
Pages (from-to)609-614
Number of pages6
JournalNature Chemistry
Volume3
Issue number8
DOIs
Publication statusPublished - Aug 2011

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Formates
Carbamates
Carbonates
Carbon Monoxide
Hydrogenation
Methanol
Alcohols
Ligands
Aromatization
Pyridine
Amines
Hydrogen
Metals
Atoms

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO 2 and CO. / Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing; Shimon, Linda J W; Milstein, David.

In: Nature Chemistry, Vol. 3, No. 8, 08.2011, p. 609-614.

Research output: Contribution to journalArticle

Balaraman, Ekambaram ; Gunanathan, Chidambaram ; Zhang, Jing ; Shimon, Linda J W ; Milstein, David. / Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO 2 and CO. In: Nature Chemistry. 2011 ; Vol. 3, No. 8. pp. 609-614.
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