Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes

A mechanistic investigation using high-pressure NMR spectroscopy

April D. Getty, Chih Cheng Tai, John Linehan, Philip G. Jessop, Marilyn M. Olmstead, Arnold L. Rheingold

Research output: Contribution to journalArticle

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Abstract

Complex cis-(PMe 3) 4RuCl(OAc) (1) acts as a catalyst for CO 2 hydrogenation into formic acid in the presence of a base and an alcohol cocatalyst. NMR spectroscopy has revealed that 1 exists in solution in equilibrium with fac-(PMe 3) 3RuCl(η 2-OAc) (2), [(PMe3)4Ru(η 2-OAc)]Cl (3a), and free PMe 3. Complex 2 was found to be a poor CO 2 hydrogenation catalyst under the conditions of catalysis used for 1. Complex 3a can be prepared by adding certain alcohols, such as MeOH, EtOH, or C 6H 5OH, to a solution of 1 in CDCl 3. The chloride ion of 3a was exchanged for the noncoordinating anion BPh 4 - or B(Ar F) 4 - (B(Ar F) 4 = tetrakis(3,5- bis(trifluoromethyl)phenyl)borate) to produce [(PMe 3) 4Ru(η 2-OAc)]BPh 4 (3b) and [(PMe 3) 4 - Ru(η 2-OAc)]B(Ar F) 4 (3c). Complexes 3b and 3c were found to be as efficient as 1 in the catalytic hydrogenation of CO 2 to formic acid in the presence of an alcohol cocatalyst. In contrast to 1,3b and 3c continued to show high catalytic activity in the absence of the alcohol cocatalyst. High-pressure NMR spectroscopy was used to investigate the mechanism of CO 2 hydrogenation via 3b,c in the presence of base. The observations were inconsistent with the previously reported phosphine-loss mechanism; a new mechanism is proposed involving an unsaturated, cationic ruthenium complex of the form [(PMe 3) 4RuH] + (B) as the active catalyst. The role of the base in this system includes not only trapping of the formic acid product but also initiation of the catalysis by aiding the conversion of 3b,c to B. Crystallographically determined structures are reported for complexes 2, 3b, {[(PMe 3) 3Ru] 2(η-Cl) 2(η0Ac)}BPh 4, and {[(PMe 3) 3Ru] 2(w-Cl) 3}Cl.

Original languageEnglish
Pages (from-to)5466-5477
Number of pages12
JournalOrganometallics
Volume28
Issue number18
DOIs
Publication statusPublished - Sep 28 2009

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formic acid
Ruthenium
Carbon Monoxide
Carbon Dioxide
Nuclear magnetic resonance spectroscopy
ruthenium
Hydrogenation
hydrogenation
carbon dioxide
alcohols
Alcohols
nuclear magnetic resonance
phosphine
catalysts
spectroscopy
Catalysis
Catalysts
catalysis
borates
phosphines

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes : A mechanistic investigation using high-pressure NMR spectroscopy. / Getty, April D.; Tai, Chih Cheng; Linehan, John; Jessop, Philip G.; Olmstead, Marilyn M.; Rheingold, Arnold L.

In: Organometallics, Vol. 28, No. 18, 28.09.2009, p. 5466-5477.

Research output: Contribution to journalArticle

Getty, April D. ; Tai, Chih Cheng ; Linehan, John ; Jessop, Philip G. ; Olmstead, Marilyn M. ; Rheingold, Arnold L. / Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes : A mechanistic investigation using high-pressure NMR spectroscopy. In: Organometallics. 2009 ; Vol. 28, No. 18. pp. 5466-5477.
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abstract = "Complex cis-(PMe 3) 4RuCl(OAc) (1) acts as a catalyst for CO 2 hydrogenation into formic acid in the presence of a base and an alcohol cocatalyst. NMR spectroscopy has revealed that 1 exists in solution in equilibrium with fac-(PMe 3) 3RuCl(η 2-OAc) (2), [(PMe3)4Ru(η 2-OAc)]Cl (3a), and free PMe 3. Complex 2 was found to be a poor CO 2 hydrogenation catalyst under the conditions of catalysis used for 1. Complex 3a can be prepared by adding certain alcohols, such as MeOH, EtOH, or C 6H 5OH, to a solution of 1 in CDCl 3. The chloride ion of 3a was exchanged for the noncoordinating anion BPh 4 - or B(Ar F) 4 - (B(Ar F) 4 = tetrakis(3,5- bis(trifluoromethyl)phenyl)borate) to produce [(PMe 3) 4Ru(η 2-OAc)]BPh 4 (3b) and [(PMe 3) 4 - Ru(η 2-OAc)]B(Ar F) 4 (3c). Complexes 3b and 3c were found to be as efficient as 1 in the catalytic hydrogenation of CO 2 to formic acid in the presence of an alcohol cocatalyst. In contrast to 1,3b and 3c continued to show high catalytic activity in the absence of the alcohol cocatalyst. High-pressure NMR spectroscopy was used to investigate the mechanism of CO 2 hydrogenation via 3b,c in the presence of base. The observations were inconsistent with the previously reported phosphine-loss mechanism; a new mechanism is proposed involving an unsaturated, cationic ruthenium complex of the form [(PMe 3) 4RuH] + (B) as the active catalyst. The role of the base in this system includes not only trapping of the formic acid product but also initiation of the catalysis by aiding the conversion of 3b,c to B. Crystallographically determined structures are reported for complexes 2, 3b, {[(PMe 3) 3Ru] 2(η-Cl) 2(η0Ac)}BPh 4, and {[(PMe 3) 3Ru] 2(w-Cl) 3}Cl.",
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N2 - Complex cis-(PMe 3) 4RuCl(OAc) (1) acts as a catalyst for CO 2 hydrogenation into formic acid in the presence of a base and an alcohol cocatalyst. NMR spectroscopy has revealed that 1 exists in solution in equilibrium with fac-(PMe 3) 3RuCl(η 2-OAc) (2), [(PMe3)4Ru(η 2-OAc)]Cl (3a), and free PMe 3. Complex 2 was found to be a poor CO 2 hydrogenation catalyst under the conditions of catalysis used for 1. Complex 3a can be prepared by adding certain alcohols, such as MeOH, EtOH, or C 6H 5OH, to a solution of 1 in CDCl 3. The chloride ion of 3a was exchanged for the noncoordinating anion BPh 4 - or B(Ar F) 4 - (B(Ar F) 4 = tetrakis(3,5- bis(trifluoromethyl)phenyl)borate) to produce [(PMe 3) 4Ru(η 2-OAc)]BPh 4 (3b) and [(PMe 3) 4 - Ru(η 2-OAc)]B(Ar F) 4 (3c). Complexes 3b and 3c were found to be as efficient as 1 in the catalytic hydrogenation of CO 2 to formic acid in the presence of an alcohol cocatalyst. In contrast to 1,3b and 3c continued to show high catalytic activity in the absence of the alcohol cocatalyst. High-pressure NMR spectroscopy was used to investigate the mechanism of CO 2 hydrogenation via 3b,c in the presence of base. The observations were inconsistent with the previously reported phosphine-loss mechanism; a new mechanism is proposed involving an unsaturated, cationic ruthenium complex of the form [(PMe 3) 4RuH] + (B) as the active catalyst. The role of the base in this system includes not only trapping of the formic acid product but also initiation of the catalysis by aiding the conversion of 3b,c to B. Crystallographically determined structures are reported for complexes 2, 3b, {[(PMe 3) 3Ru] 2(η-Cl) 2(η0Ac)}BPh 4, and {[(PMe 3) 3Ru] 2(w-Cl) 3}Cl.

AB - Complex cis-(PMe 3) 4RuCl(OAc) (1) acts as a catalyst for CO 2 hydrogenation into formic acid in the presence of a base and an alcohol cocatalyst. NMR spectroscopy has revealed that 1 exists in solution in equilibrium with fac-(PMe 3) 3RuCl(η 2-OAc) (2), [(PMe3)4Ru(η 2-OAc)]Cl (3a), and free PMe 3. Complex 2 was found to be a poor CO 2 hydrogenation catalyst under the conditions of catalysis used for 1. Complex 3a can be prepared by adding certain alcohols, such as MeOH, EtOH, or C 6H 5OH, to a solution of 1 in CDCl 3. The chloride ion of 3a was exchanged for the noncoordinating anion BPh 4 - or B(Ar F) 4 - (B(Ar F) 4 = tetrakis(3,5- bis(trifluoromethyl)phenyl)borate) to produce [(PMe 3) 4Ru(η 2-OAc)]BPh 4 (3b) and [(PMe 3) 4 - Ru(η 2-OAc)]B(Ar F) 4 (3c). Complexes 3b and 3c were found to be as efficient as 1 in the catalytic hydrogenation of CO 2 to formic acid in the presence of an alcohol cocatalyst. In contrast to 1,3b and 3c continued to show high catalytic activity in the absence of the alcohol cocatalyst. High-pressure NMR spectroscopy was used to investigate the mechanism of CO 2 hydrogenation via 3b,c in the presence of base. The observations were inconsistent with the previously reported phosphine-loss mechanism; a new mechanism is proposed involving an unsaturated, cationic ruthenium complex of the form [(PMe 3) 4RuH] + (B) as the active catalyst. The role of the base in this system includes not only trapping of the formic acid product but also initiation of the catalysis by aiding the conversion of 3b,c to B. Crystallographically determined structures are reported for complexes 2, 3b, {[(PMe 3) 3Ru] 2(η-Cl) 2(η0Ac)}BPh 4, and {[(PMe 3) 3Ru] 2(w-Cl) 3}Cl.

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