Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core

Arkadi Vigalok; Yehoshoa Ben-David; David Milstein

doi:10.1021/om950830z

Complexation of N₂, H₂, CO₂, and ethylene to a T-shaped rhodium(I) core

Arkadi Vigalok, Yehoshoa Ben-David, David Milstein

Weizmann Institute of Science, Israel

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

101 Citations (Scopus)

Abstract

The new rhodium-dinitrogen complex Rh(N₂)[HC(CH₂CH₂P(t-Bu)₂) ₂] (2) was prepared by elimination of HCl with sodium hydride from the hydrido chloride HRh(Cl)[HC(CH₂CH₂P(t-Bu)₂)₂] (1). Complex 2 reacts with various small gaseous molecules, giving rise to the new complexes Rh(X)[HC(CH₂CH₂P(t-Bu)₂)₂], X = H₂ (3), C₂H₄ (4), CO₂ (5). The first 16 electron rhodium-carbon dioxide complex 5 is spectroscopically characterized. All the transformations are reversible in the presence of free nitrogen. The thermodynamic parameters for these equilibria reactions have been evaluated. It is found that at 25°C formation of the dihydrogen complex 3 is about 1.24 kcal/mol more favorable than formation of its dinitrogen analogue 2, whereas formation of the carbon dioxide (5) and, surprisingly, ethylene (4) complexes is less favorable than 2 by 2.97 and 1.57 kcal/mol, respectively, yielding the ligating ability to the Rh(I) T-shaped core L = H₂ > N₂ > C₂H₄ > (CO₂). The new hydrido formate HRh(O₂CH)[HC(CH₂CH₂P(t-Bu)₂) ₂] (7) can be obtained either by reaction of the dihydrogen complex 3 with CO₂ or from the carbon dioxide complex 5 with hydrogen.

Original language	English
Pages (from-to)	1839-1844
Number of pages	6
Journal	Organometallics
Volume	15
Issue number	7
DOIs	https://doi.org/10.1021/om950830z
Publication status	Published - Apr 2 1996

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{279631466571421783b6bc85736c252e,

title = "Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core",

abstract = "The new rhodium-dinitrogen complex Rh(N2)[HC(CH2CH2P(t-Bu)2) 2] (2) was prepared by elimination of HCl with sodium hydride from the hydrido chloride HRh(Cl)[HC(CH2CH2P(t-Bu)2)2] (1). Complex 2 reacts with various small gaseous molecules, giving rise to the new complexes Rh(X)[HC(CH2CH2P(t-Bu)2)2], X = H2 (3), C2H4 (4), CO2 (5). The first 16 electron rhodium-carbon dioxide complex 5 is spectroscopically characterized. All the transformations are reversible in the presence of free nitrogen. The thermodynamic parameters for these equilibria reactions have been evaluated. It is found that at 25°C formation of the dihydrogen complex 3 is about 1.24 kcal/mol more favorable than formation of its dinitrogen analogue 2, whereas formation of the carbon dioxide (5) and, surprisingly, ethylene (4) complexes is less favorable than 2 by 2.97 and 1.57 kcal/mol, respectively, yielding the ligating ability to the Rh(I) T-shaped core L = H2 > N2 > C2H4 > (CO2). The new hydrido formate HRh(O2CH)[HC(CH2CH2P(t-Bu)2) 2] (7) can be obtained either by reaction of the dihydrogen complex 3 with CO2 or from the carbon dioxide complex 5 with hydrogen.",

author = "Arkadi Vigalok and Yehoshoa Ben-David and David Milstein",

year = "1996",

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T1 - Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core

AU - Vigalok, Arkadi

AU - Ben-David, Yehoshoa

AU - Milstein, David

PY - 1996/4/2

Y1 - 1996/4/2

N2 - The new rhodium-dinitrogen complex Rh(N2)[HC(CH2CH2P(t-Bu)2) 2] (2) was prepared by elimination of HCl with sodium hydride from the hydrido chloride HRh(Cl)[HC(CH2CH2P(t-Bu)2)2] (1). Complex 2 reacts with various small gaseous molecules, giving rise to the new complexes Rh(X)[HC(CH2CH2P(t-Bu)2)2], X = H2 (3), C2H4 (4), CO2 (5). The first 16 electron rhodium-carbon dioxide complex 5 is spectroscopically characterized. All the transformations are reversible in the presence of free nitrogen. The thermodynamic parameters for these equilibria reactions have been evaluated. It is found that at 25°C formation of the dihydrogen complex 3 is about 1.24 kcal/mol more favorable than formation of its dinitrogen analogue 2, whereas formation of the carbon dioxide (5) and, surprisingly, ethylene (4) complexes is less favorable than 2 by 2.97 and 1.57 kcal/mol, respectively, yielding the ligating ability to the Rh(I) T-shaped core L = H2 > N2 > C2H4 > (CO2). The new hydrido formate HRh(O2CH)[HC(CH2CH2P(t-Bu)2) 2] (7) can be obtained either by reaction of the dihydrogen complex 3 with CO2 or from the carbon dioxide complex 5 with hydrogen.

AB - The new rhodium-dinitrogen complex Rh(N2)[HC(CH2CH2P(t-Bu)2) 2] (2) was prepared by elimination of HCl with sodium hydride from the hydrido chloride HRh(Cl)[HC(CH2CH2P(t-Bu)2)2] (1). Complex 2 reacts with various small gaseous molecules, giving rise to the new complexes Rh(X)[HC(CH2CH2P(t-Bu)2)2], X = H2 (3), C2H4 (4), CO2 (5). The first 16 electron rhodium-carbon dioxide complex 5 is spectroscopically characterized. All the transformations are reversible in the presence of free nitrogen. The thermodynamic parameters for these equilibria reactions have been evaluated. It is found that at 25°C formation of the dihydrogen complex 3 is about 1.24 kcal/mol more favorable than formation of its dinitrogen analogue 2, whereas formation of the carbon dioxide (5) and, surprisingly, ethylene (4) complexes is less favorable than 2 by 2.97 and 1.57 kcal/mol, respectively, yielding the ligating ability to the Rh(I) T-shaped core L = H2 > N2 > C2H4 > (CO2). The new hydrido formate HRh(O2CH)[HC(CH2CH2P(t-Bu)2) 2] (7) can be obtained either by reaction of the dihydrogen complex 3 with CO2 or from the carbon dioxide complex 5 with hydrogen.

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