Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH2(O2COH)(P(i-Pr)3)2

T. Yoshida; T. Okano; S. Otsuka; David L. Thorn; James A. Ibers

doi:10.1021/ja00509a029

Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH₂(O₂COH)(P(i-Pr)₃)₂

T. Yoshida, T. Okano, S. Otsuka, David L. Thorn, James A. Ibers

Chemistry

Research output: Contribution to journal › Article › peer-review

137 Scopus citations

Abstract

Reaction of Rh(I) -hydride complexes RhH(P(i-Pr)₃)₃, RhH(N₂)(PPh(t-Bu)₂)₂, and Rh₂H₂(μ-N₂)(P(c-C₆H₁₁)₃)₄with CO₂in the presence of H₂O has been found to afford novel dihydrido bicarbonato complexes RhH₂(O₂COH)L₂(1,L = P(i-Pr)₃; 2, L = PPh(t-Bu)₂; 3, L = P(c-C₆H₁₁)₃). The crystal and molecular structure of 1 has been determined at -160°C. The complex RhH₂(O₂COH)(P(i-Pr)₃)₂(1) crystallizes in the monoclinic space group C_2n-P2₁/c, with four formula units in a cell of dimensions a = 15.82 (1) Å, b = 10.88 (1) Å, c = I 5.49 (1) Å, β = 114.5 (1)°, V = 2428 Å³. In the solid state 1 consists of distorted octahedral Rh(lll) centers coupled by intermolecular hydrogen bonding between bicarbonato ligands. These dihydrido bicarbonato complexes, and analogous dihydrido formato complexes, reduce CO₂to form Rh(l) carbonyl bicarbonato and formato complexes and H₂O.

Original language	English (US)
Pages (from-to)	4212-4221
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	101
Issue number	15
DOIs	https://doi.org/10.1021/ja00509a029
State	Published - Jul 1 1979

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Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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@article{e515637cc67f4f8daa5ca02e62a54579,

title = "Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH2(O2COH)(P(i-Pr)3)2",

abstract = "Reaction of Rh(I) -hydride complexes RhH(P(i-Pr)3)3, RhH(N2)(PPh(t-Bu)2)2, and Rh2H2(μ-N2)(P(c-C6H11)3)4with CO2in the presence of H2O has been found to afford novel dihydrido bicarbonato complexes RhH2(O2COH)L2(1,L = P(i-Pr)3; 2, L = PPh(t-Bu)2; 3, L = P(c-C6H11)3). The crystal and molecular structure of 1 has been determined at -160°C. The complex RhH2(O2COH)(P(i-Pr)3)2(1) crystallizes in the monoclinic space group C2n-P21/c, with four formula units in a cell of dimensions a = 15.82 (1) {\AA}, b = 10.88 (1) {\AA}, c = I 5.49 (1) {\AA}, β = 114.5 (1)°, V = 2428 {\AA}3. In the solid state 1 consists of distorted octahedral Rh(lll) centers coupled by intermolecular hydrogen bonding between bicarbonato ligands. These dihydrido bicarbonato complexes, and analogous dihydrido formato complexes, reduce CO2to form Rh(l) carbonyl bicarbonato and formato complexes and H2O.",

author = "T. Yoshida and T. Okano and S. Otsuka and Thorn, {David L.} and Ibers, {James A.}",

year = "1979",

month = jul,

day = "1",

doi = "10.1021/ja00509a029",

language = "English (US)",

volume = "101",

pages = "4212--4221",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "15",

}

Yoshida, T, Okano, T, Otsuka, S, Thorn, DL & Ibers, JA 1979, 'Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH₂(O₂COH)(P(i-Pr)₃)₂', Journal of the American Chemical Society, vol. 101, no. 15, pp. 4212-4221. https://doi.org/10.1021/ja00509a029

Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH₂(O₂COH)(P(i-Pr)₃)₂. / Yoshida, T.; Okano, T.; Otsuka, S. et al.
In: Journal of the American Chemical Society, Vol. 101, No. 15, 01.07.1979, p. 4212-4221.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH2(O2COH)(P(i-Pr)3)2

AU - Yoshida, T.

AU - Okano, T.

AU - Otsuka, S.

AU - Thorn, David L.

AU - Ibers, James A.

PY - 1979/7/1

Y1 - 1979/7/1

N2 - Reaction of Rh(I) -hydride complexes RhH(P(i-Pr)3)3, RhH(N2)(PPh(t-Bu)2)2, and Rh2H2(μ-N2)(P(c-C6H11)3)4with CO2in the presence of H2O has been found to afford novel dihydrido bicarbonato complexes RhH2(O2COH)L2(1,L = P(i-Pr)3; 2, L = PPh(t-Bu)2; 3, L = P(c-C6H11)3). The crystal and molecular structure of 1 has been determined at -160°C. The complex RhH2(O2COH)(P(i-Pr)3)2(1) crystallizes in the monoclinic space group C2n-P21/c, with four formula units in a cell of dimensions a = 15.82 (1) Å, b = 10.88 (1) Å, c = I 5.49 (1) Å, β = 114.5 (1)°, V = 2428 Å3. In the solid state 1 consists of distorted octahedral Rh(lll) centers coupled by intermolecular hydrogen bonding between bicarbonato ligands. These dihydrido bicarbonato complexes, and analogous dihydrido formato complexes, reduce CO2to form Rh(l) carbonyl bicarbonato and formato complexes and H2O.

AB - Reaction of Rh(I) -hydride complexes RhH(P(i-Pr)3)3, RhH(N2)(PPh(t-Bu)2)2, and Rh2H2(μ-N2)(P(c-C6H11)3)4with CO2in the presence of H2O has been found to afford novel dihydrido bicarbonato complexes RhH2(O2COH)L2(1,L = P(i-Pr)3; 2, L = PPh(t-Bu)2; 3, L = P(c-C6H11)3). The crystal and molecular structure of 1 has been determined at -160°C. The complex RhH2(O2COH)(P(i-Pr)3)2(1) crystallizes in the monoclinic space group C2n-P21/c, with four formula units in a cell of dimensions a = 15.82 (1) Å, b = 10.88 (1) Å, c = I 5.49 (1) Å, β = 114.5 (1)°, V = 2428 Å3. In the solid state 1 consists of distorted octahedral Rh(lll) centers coupled by intermolecular hydrogen bonding between bicarbonato ligands. These dihydrido bicarbonato complexes, and analogous dihydrido formato complexes, reduce CO2to form Rh(l) carbonyl bicarbonato and formato complexes and H2O.

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U2 - 10.1021/ja00509a029

DO - 10.1021/ja00509a029

M3 - Article

AN - SCOPUS:0001157349

SN - 0002-7863

VL - 101

SP - 4212

EP - 4221

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 15

ER -

Hydration and Reduction of Carbon Dioxide by Rhodium Hydride Compounds. Preparation and Reactions of Rhodium Bicarbonate and Formate Complexes, and the Molecular Structure of RhH₂(O₂COH)(P(i-Pr)₃)₂

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