Formation and characterization of water-soluble hydrido-ruthenium(II) complexes of 1,3,5-triaza-7-phosphaadamantane and their catalytic activity in hydrogenation of CO2 and HCO3 - in aqueous solution

G. Laurenczy, F. Joo, L. Nadasdi

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Abstract

The water-soluble tertiary phosphine complex of ruthenium(II), [RuCl2(PTA)4], (PTA = 1,3,5-triaza-7-phosphaadamantane) was used as catalyst precursor for hydrogenation of CO2 and bicarbonate in aqueous solution, in the absence of amine or other additives, under mild conditions. Reaction of [RuCl2(PTA)4] and H2 (60 bar) gives the hydrides [RuH2(PTA)4] (at pH = 12.0) and [RuH(PTA)4X] (X = Cl- or H2O) (at pH = 2.0). In presence of excess PTA, formation of the unparalleled cationic pentakis-phosphino species, [HRu(PTA)5]+, was unambiguously established by 1H and 31P NMR measurements. The same hydrides were observed when [Ru-(H2O)6][tos]2 (tos = toluene-4-sulfonate) reacted with PTA under H2 pressure. The rate of CO2 hydrogenation strongly depends on the pH. The highest initial reaction rate (TOF = 807.3 h-1) was determined for a 10% HCO3 -/90% CO2 mixture (pH = 5.86), whereas the reduction was very slow both at low and high pH (CO2 and Na2CO3 solutions, respectively). 1H and 31P NMR studies together with the kinetic measurements suggested that HCO3 - was the real substrate and [RuH(PTA)4X] the catalytically active hydride species in this reaction. Hydrogenation of HCO3 - showed an induction period which could be ascribed to the slow formation of the catalytically active hydride species.

Original languageEnglish
Pages (from-to)5083-5088
Number of pages6
JournalInorganic Chemistry
Volume39
Issue number22
DOIs
Publication statusPublished - Oct 30 2000

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Ruthenium
Hydrides
ruthenium
Hydrogenation
hydrogenation
catalytic activity
Catalyst activity
hydrides
aqueous solutions
phosphine
Water
water
Nuclear magnetic resonance
Bicarbonates
nuclear magnetic resonance
Reaction rates
Amines
sulfonates
phosphines
toluene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Formation and characterization of water-soluble hydrido-ruthenium(II) complexes of 1,3,5-triaza-7-phosphaadamantane and their catalytic activity in hydrogenation of CO2 and HCO3 - in aqueous solution",
abstract = "The water-soluble tertiary phosphine complex of ruthenium(II), [RuCl2(PTA)4], (PTA = 1,3,5-triaza-7-phosphaadamantane) was used as catalyst precursor for hydrogenation of CO2 and bicarbonate in aqueous solution, in the absence of amine or other additives, under mild conditions. Reaction of [RuCl2(PTA)4] and H2 (60 bar) gives the hydrides [RuH2(PTA)4] (at pH = 12.0) and [RuH(PTA)4X] (X = Cl- or H2O) (at pH = 2.0). In presence of excess PTA, formation of the unparalleled cationic pentakis-phosphino species, [HRu(PTA)5]+, was unambiguously established by 1H and 31P NMR measurements. The same hydrides were observed when [Ru-(H2O)6][tos]2 (tos = toluene-4-sulfonate) reacted with PTA under H2 pressure. The rate of CO2 hydrogenation strongly depends on the pH. The highest initial reaction rate (TOF = 807.3 h-1) was determined for a 10{\%} HCO3 -/90{\%} CO2 mixture (pH = 5.86), whereas the reduction was very slow both at low and high pH (CO2 and Na2CO3 solutions, respectively). 1H and 31P NMR studies together with the kinetic measurements suggested that HCO3 - was the real substrate and [RuH(PTA)4X] the catalytically active hydride species in this reaction. Hydrogenation of HCO3 - showed an induction period which could be ascribed to the slow formation of the catalytically active hydride species.",
author = "G. Laurenczy and F. Joo and L. Nadasdi",
year = "2000",
month = "10",
day = "30",
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language = "English",
volume = "39",
pages = "5083--5088",
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T1 - Formation and characterization of water-soluble hydrido-ruthenium(II) complexes of 1,3,5-triaza-7-phosphaadamantane and their catalytic activity in hydrogenation of CO2 and HCO3 - in aqueous solution

AU - Laurenczy, G.

AU - Joo, F.

AU - Nadasdi, L.

PY - 2000/10/30

Y1 - 2000/10/30

N2 - The water-soluble tertiary phosphine complex of ruthenium(II), [RuCl2(PTA)4], (PTA = 1,3,5-triaza-7-phosphaadamantane) was used as catalyst precursor for hydrogenation of CO2 and bicarbonate in aqueous solution, in the absence of amine or other additives, under mild conditions. Reaction of [RuCl2(PTA)4] and H2 (60 bar) gives the hydrides [RuH2(PTA)4] (at pH = 12.0) and [RuH(PTA)4X] (X = Cl- or H2O) (at pH = 2.0). In presence of excess PTA, formation of the unparalleled cationic pentakis-phosphino species, [HRu(PTA)5]+, was unambiguously established by 1H and 31P NMR measurements. The same hydrides were observed when [Ru-(H2O)6][tos]2 (tos = toluene-4-sulfonate) reacted with PTA under H2 pressure. The rate of CO2 hydrogenation strongly depends on the pH. The highest initial reaction rate (TOF = 807.3 h-1) was determined for a 10% HCO3 -/90% CO2 mixture (pH = 5.86), whereas the reduction was very slow both at low and high pH (CO2 and Na2CO3 solutions, respectively). 1H and 31P NMR studies together with the kinetic measurements suggested that HCO3 - was the real substrate and [RuH(PTA)4X] the catalytically active hydride species in this reaction. Hydrogenation of HCO3 - showed an induction period which could be ascribed to the slow formation of the catalytically active hydride species.

AB - The water-soluble tertiary phosphine complex of ruthenium(II), [RuCl2(PTA)4], (PTA = 1,3,5-triaza-7-phosphaadamantane) was used as catalyst precursor for hydrogenation of CO2 and bicarbonate in aqueous solution, in the absence of amine or other additives, under mild conditions. Reaction of [RuCl2(PTA)4] and H2 (60 bar) gives the hydrides [RuH2(PTA)4] (at pH = 12.0) and [RuH(PTA)4X] (X = Cl- or H2O) (at pH = 2.0). In presence of excess PTA, formation of the unparalleled cationic pentakis-phosphino species, [HRu(PTA)5]+, was unambiguously established by 1H and 31P NMR measurements. The same hydrides were observed when [Ru-(H2O)6][tos]2 (tos = toluene-4-sulfonate) reacted with PTA under H2 pressure. The rate of CO2 hydrogenation strongly depends on the pH. The highest initial reaction rate (TOF = 807.3 h-1) was determined for a 10% HCO3 -/90% CO2 mixture (pH = 5.86), whereas the reduction was very slow both at low and high pH (CO2 and Na2CO3 solutions, respectively). 1H and 31P NMR studies together with the kinetic measurements suggested that HCO3 - was the real substrate and [RuH(PTA)4X] the catalytically active hydride species in this reaction. Hydrogenation of HCO3 - showed an induction period which could be ascribed to the slow formation of the catalytically active hydride species.

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