In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide

Chih Cheng Tai, Justine Pitts, John Linehan, A. Denise Main, Pradip Munshi, Philip G. Jessop

Research output: Contribution to journalArticle

86 Citations (Scopus)

Abstract

A total of 44 different phosphines were tested, in combination with [RuCl2(C6H6)]2 and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of C02 to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe3, PPhMe2, dppm, dppe, and cis- and trans-Ph2PCH=CHPPh2. The in situ catalysts prepared from [RuCl2-(C6H6)]2 and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O2CMe)(PMe3)4. There was no correlation between the basicity of monophosphines (PR3) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ 31p NMR spectroscopy showed that trans-Ru(H)2(dppm)2, trans-RuCl2(dppm)2, trans-RuHCl(dppm)2, cis-Ru(H)(O2CH)(dppm)2, and cis-Ru-(O2CH)2(dppm)2 are produced as the major metal-containing species in reactions of dppm with [RuCl2(C6H6)]2 under catalytic conditions at 50°C.

Original languageEnglish
Pages (from-to)1606-1614
Number of pages9
JournalInorganic Chemistry
Volume41
Issue number6
DOIs
Publication statusPublished - Mar 25 2002

Fingerprint

Ruthenium
Carbon Dioxide
ruthenium
Hydrogenation
hydrogenation
carbon dioxide
formic acid
catalysts
Catalysts
phosphine
phosphines
Phosphines
Ligands
ligands
Alkalinity
Nuclear magnetic resonance spectroscopy
Metals
trends
nuclear magnetic resonance
metals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide. / Tai, Chih Cheng; Pitts, Justine; Linehan, John; Main, A. Denise; Munshi, Pradip; Jessop, Philip G.

In: Inorganic Chemistry, Vol. 41, No. 6, 25.03.2002, p. 1606-1614.

Research output: Contribution to journalArticle

Tai, Chih Cheng ; Pitts, Justine ; Linehan, John ; Main, A. Denise ; Munshi, Pradip ; Jessop, Philip G. / In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 6. pp. 1606-1614.
@article{ebdec3403a14416db141b788775080df,
title = "In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide",
abstract = "A total of 44 different phosphines were tested, in combination with [RuCl2(C6H6)]2 and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of C02 to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe3, PPhMe2, dppm, dppe, and cis- and trans-Ph2PCH=CHPPh2. The in situ catalysts prepared from [RuCl2-(C6H6)]2 and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O2CMe)(PMe3)4. There was no correlation between the basicity of monophosphines (PR3) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ 31p NMR spectroscopy showed that trans-Ru(H)2(dppm)2, trans-RuCl2(dppm)2, trans-RuHCl(dppm)2, cis-Ru(H)(O2CH)(dppm)2, and cis-Ru-(O2CH)2(dppm)2 are produced as the major metal-containing species in reactions of dppm with [RuCl2(C6H6)]2 under catalytic conditions at 50°C.",
author = "Tai, {Chih Cheng} and Justine Pitts and John Linehan and Main, {A. Denise} and Pradip Munshi and Jessop, {Philip G.}",
year = "2002",
month = "3",
day = "25",
doi = "10.1021/ic010866l",
language = "English",
volume = "41",
pages = "1606--1614",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - In situ formation of ruthenium catalysts for the homogeneous hydrogenation of carbon dioxide

AU - Tai, Chih Cheng

AU - Pitts, Justine

AU - Linehan, John

AU - Main, A. Denise

AU - Munshi, Pradip

AU - Jessop, Philip G.

PY - 2002/3/25

Y1 - 2002/3/25

N2 - A total of 44 different phosphines were tested, in combination with [RuCl2(C6H6)]2 and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of C02 to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe3, PPhMe2, dppm, dppe, and cis- and trans-Ph2PCH=CHPPh2. The in situ catalysts prepared from [RuCl2-(C6H6)]2 and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O2CMe)(PMe3)4. There was no correlation between the basicity of monophosphines (PR3) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ 31p NMR spectroscopy showed that trans-Ru(H)2(dppm)2, trans-RuCl2(dppm)2, trans-RuHCl(dppm)2, cis-Ru(H)(O2CH)(dppm)2, and cis-Ru-(O2CH)2(dppm)2 are produced as the major metal-containing species in reactions of dppm with [RuCl2(C6H6)]2 under catalytic conditions at 50°C.

AB - A total of 44 different phosphines were tested, in combination with [RuCl2(C6H6)]2 and three other Ru(II) precursors, for their ability to form active catalysts for the hydrogenation of C02 to formic acid. Half (22) of the ligands formed catalysts of significant activity, and only 6 resulted in very high rates of production of formic acid. These were PMe3, PPhMe2, dppm, dppe, and cis- and trans-Ph2PCH=CHPPh2. The in situ catalysts prepared from [RuCl2-(C6H6)]2 and any of these 6 phosphine ligands were found to be at least as efficient as the isolated catalyst RuCl(O2CMe)(PMe3)4. There was no correlation between the basicity of monophosphines (PR3) and the activity of the catalysts formed from them. However, weakly basic diphosphines formed highly active catalysts only if their bite angles were small, while more strongly basic diphosphines had the opposite trend. In situ 31p NMR spectroscopy showed that trans-Ru(H)2(dppm)2, trans-RuCl2(dppm)2, trans-RuHCl(dppm)2, cis-Ru(H)(O2CH)(dppm)2, and cis-Ru-(O2CH)2(dppm)2 are produced as the major metal-containing species in reactions of dppm with [RuCl2(C6H6)]2 under catalytic conditions at 50°C.

UR - http://www.scopus.com/inward/record.url?scp=0037170837&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037170837&partnerID=8YFLogxK

U2 - 10.1021/ic010866l

DO - 10.1021/ic010866l

M3 - Article

VL - 41

SP - 1606

EP - 1614

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 6

ER -