Discovery of environmentally benign catalytic reactions of alcohols catalyzed by pyridine-based pincer Ru complexes, based on metal-ligand cooperation

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Abstract

We have developed a new mode of metal-ligand cooperation, based on aromatization-dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C-H bonds by PNP Ir complexes. This type of metal-ligand cooperation plays a key role in the recently discovered environmentally benign reactions of alcohols, catalyzed by PNP and PNN pincer complexes of ruthenium, including (a) dehydrogenation of secondary alcohols to ketones (b) dehydrogenative coupling of primary alcohols to form esters and H2 (c) hydrogenation of esters to alcohols under mild conditions (d) unprecedented amide synthesis: catalytic coupling of amines with alcohols, with liberation of H2. Ligand modification in the latter reaction has led to unprecedented synthesis of imines with H2 liberation. These reactions are very efficient, proceed under neutral conditions and produce no waste.

Original languageEnglish
Pages (from-to)915-923
Number of pages9
JournalTopics in Catalysis
Volume53
Issue number13-14
DOIs
Publication statusPublished - Aug 2010

Fingerprint

Pyridine
Alcohols
Metals
Ligands
Esters
Aromatization
Imines
Ruthenium
Dehydrogenation
Ketones
Amides
Hydrogenation
Amines
Chemical activation
pyridine

Keywords

  • Acohols
  • Amides
  • Amines
  • C-H activation
  • Catalysis
  • Dehydrogenative coupling
  • Hydrogen
  • Imines
  • Iridium
  • Metal-ligand cooperation
  • O-H activation
  • Pincer complexes
  • PNN
  • PNP
  • Ruthenium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Discovery of environmentally benign catalytic reactions of alcohols catalyzed by pyridine-based pincer Ru complexes, based on metal-ligand cooperation",
abstract = "We have developed a new mode of metal-ligand cooperation, based on aromatization-dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C-H bonds by PNP Ir complexes. This type of metal-ligand cooperation plays a key role in the recently discovered environmentally benign reactions of alcohols, catalyzed by PNP and PNN pincer complexes of ruthenium, including (a) dehydrogenation of secondary alcohols to ketones (b) dehydrogenative coupling of primary alcohols to form esters and H2 (c) hydrogenation of esters to alcohols under mild conditions (d) unprecedented amide synthesis: catalytic coupling of amines with alcohols, with liberation of H2. Ligand modification in the latter reaction has led to unprecedented synthesis of imines with H2 liberation. These reactions are very efficient, proceed under neutral conditions and produce no waste.",
keywords = "Acohols, Amides, Amines, C-H activation, Catalysis, Dehydrogenative coupling, Hydrogen, Imines, Iridium, Metal-ligand cooperation, O-H activation, Pincer complexes, PNN, PNP, Ruthenium",
author = "David Milstein",
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AU - Milstein, David

PY - 2010/8

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N2 - We have developed a new mode of metal-ligand cooperation, based on aromatization-dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C-H bonds by PNP Ir complexes. This type of metal-ligand cooperation plays a key role in the recently discovered environmentally benign reactions of alcohols, catalyzed by PNP and PNN pincer complexes of ruthenium, including (a) dehydrogenation of secondary alcohols to ketones (b) dehydrogenative coupling of primary alcohols to form esters and H2 (c) hydrogenation of esters to alcohols under mild conditions (d) unprecedented amide synthesis: catalytic coupling of amines with alcohols, with liberation of H2. Ligand modification in the latter reaction has led to unprecedented synthesis of imines with H2 liberation. These reactions are very efficient, proceed under neutral conditions and produce no waste.

AB - We have developed a new mode of metal-ligand cooperation, based on aromatization-dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C-H bonds by PNP Ir complexes. This type of metal-ligand cooperation plays a key role in the recently discovered environmentally benign reactions of alcohols, catalyzed by PNP and PNN pincer complexes of ruthenium, including (a) dehydrogenation of secondary alcohols to ketones (b) dehydrogenative coupling of primary alcohols to form esters and H2 (c) hydrogenation of esters to alcohols under mild conditions (d) unprecedented amide synthesis: catalytic coupling of amines with alcohols, with liberation of H2. Ligand modification in the latter reaction has led to unprecedented synthesis of imines with H2 liberation. These reactions are very efficient, proceed under neutral conditions and produce no waste.

KW - Acohols

KW - Amides

KW - Amines

KW - C-H activation

KW - Catalysis

KW - Dehydrogenative coupling

KW - Hydrogen

KW - Imines

KW - Iridium

KW - Metal-ligand cooperation

KW - O-H activation

KW - Pincer complexes

KW - PNN

KW - PNP

KW - Ruthenium

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U2 - 10.1007/s11244-010-9523-7

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EP - 923

JO - Topics in Catalysis

JF - Topics in Catalysis

SN - 1022-5528

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