Reactivity of Some Transition-Metal Systems toward Liquid Carbon Dioxide

Michael G. Mason; James A Ibers

doi:10.1021/ja00383a026

Reactivity of Some Transition-Metal Systems toward Liquid Carbon Dioxide

Michael G. Mason, James A Ibers^*

^*Corresponding author for this work

Chemistry

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56 Scopus citations

Abstract

The reactivity of several transition-metal complexes toward liquid CO₂ has been investigated as a means of screening such complexes for their ability to bind CO₂. Although the known Ni(CO₂)(PCy₃)₂ complex was prepared by the reaction of [Ni(PCy₃)₂]₂(μ-N₂) with CO₂(l), the compounds Pd(PCy₃)₂ and Pt(PCy₃)₂ do not react with CO₂(1) to afford CO₂ complexes. But the compound Pt(PCy₃)₂ does react with wet CO₂ to afford PtH(O₂COH)(PCy₃)₂, a bicarbonato complex. Similar reactivity was seen for W(CO)₃(PCy₃)₂, which produces WH(O₂COH)(CO)₃(PCy₃)₂ in wet CO₂(l). The compounds Na[Co(N₂)(PEt₂Ph)₃] and [Co(PEt₂Ph)₃]₂(μ-N₂) react with CO₂(l) to form complexes that contain carbonyl and carbonato ligands. Peroxocarbonato complexes, IrR(OCO₃)(CO)(PPh₃)₂ (R = Me, Ph), were prepared from IrR(O₂)(CO)(PPh₃)₂ with CO₂(l).

Original language	English (US)
Pages (from-to)	5153-5157
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	104
Issue number	19
DOIs	https://doi.org/10.1021/ja00383a026
State	Published - Jan 1 1982

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ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Mason, M. G., & Ibers, J. A. (1982). Reactivity of Some Transition-Metal Systems toward Liquid Carbon Dioxide. Journal of the American Chemical Society, 104(19), 5153-5157. https://doi.org/10.1021/ja00383a026

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abstract = "The reactivity of several transition-metal complexes toward liquid CO2 has been investigated as a means of screening such complexes for their ability to bind CO2. Although the known Ni(CO2)(PCy3)2 complex was prepared by the reaction of [Ni(PCy3)2]2(μ-N2) with CO2(l), the compounds Pd(PCy3)2 and Pt(PCy3)2 do not react with CO2(1) to afford CO2 complexes. But the compound Pt(PCy3)2 does react with wet CO2 to afford PtH(O2COH)(PCy3)2, a bicarbonato complex. Similar reactivity was seen for W(CO)3(PCy3)2, which produces WH(O2COH)(CO)3(PCy3)2 in wet CO2(l). The compounds Na[Co(N2)(PEt2Ph)3] and [Co(PEt2Ph)3]2(μ-N2) react with CO2(l) to form complexes that contain carbonyl and carbonato ligands. Peroxocarbonato complexes, IrR(OCO3)(CO)(PPh3)2 (R = Me, Ph), were prepared from IrR(O2)(CO)(PPh3)2 with CO2(l).",

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N2 - The reactivity of several transition-metal complexes toward liquid CO2 has been investigated as a means of screening such complexes for their ability to bind CO2. Although the known Ni(CO2)(PCy3)2 complex was prepared by the reaction of [Ni(PCy3)2]2(μ-N2) with CO2(l), the compounds Pd(PCy3)2 and Pt(PCy3)2 do not react with CO2(1) to afford CO2 complexes. But the compound Pt(PCy3)2 does react with wet CO2 to afford PtH(O2COH)(PCy3)2, a bicarbonato complex. Similar reactivity was seen for W(CO)3(PCy3)2, which produces WH(O2COH)(CO)3(PCy3)2 in wet CO2(l). The compounds Na[Co(N2)(PEt2Ph)3] and [Co(PEt2Ph)3]2(μ-N2) react with CO2(l) to form complexes that contain carbonyl and carbonato ligands. Peroxocarbonato complexes, IrR(OCO3)(CO)(PPh3)2 (R = Me, Ph), were prepared from IrR(O2)(CO)(PPh3)2 with CO2(l).

AB - The reactivity of several transition-metal complexes toward liquid CO2 has been investigated as a means of screening such complexes for their ability to bind CO2. Although the known Ni(CO2)(PCy3)2 complex was prepared by the reaction of [Ni(PCy3)2]2(μ-N2) with CO2(l), the compounds Pd(PCy3)2 and Pt(PCy3)2 do not react with CO2(1) to afford CO2 complexes. But the compound Pt(PCy3)2 does react with wet CO2 to afford PtH(O2COH)(PCy3)2, a bicarbonato complex. Similar reactivity was seen for W(CO)3(PCy3)2, which produces WH(O2COH)(CO)3(PCy3)2 in wet CO2(l). The compounds Na[Co(N2)(PEt2Ph)3] and [Co(PEt2Ph)3]2(μ-N2) react with CO2(l) to form complexes that contain carbonyl and carbonato ligands. Peroxocarbonato complexes, IrR(OCO3)(CO)(PPh3)2 (R = Me, Ph), were prepared from IrR(O2)(CO)(PPh3)2 with CO2(l).

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