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

Arkadi Vigalok, Yehoshoa Ben-David, David Milstein

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)1839-1844
Number of pages6
JournalOrganometallics
Volume15
Issue number7
Publication statusPublished - Apr 2 1996

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Rhodium
Complexation
rhodium
Carbon Dioxide
carbon dioxide
formic acid
ethylene
sodium hydrides
formates
Chlorides
Hydrogen
elimination
Nitrogen
chlorides
Thermodynamics
analogs
nitrogen
thermodynamics
Molecules
Electrons

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core. / Vigalok, Arkadi; Ben-David, Yehoshoa; Milstein, David.

In: Organometallics, Vol. 15, No. 7, 02.04.1996, p. 1839-1844.

Research output: Contribution to journalArticle

Vigalok, A, Ben-David, Y & Milstein, D 1996, 'Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core', Organometallics, vol. 15, no. 7, pp. 1839-1844.
Vigalok, Arkadi ; Ben-David, Yehoshoa ; Milstein, David. / Complexation of N2, H2, CO2, and ethylene to a T-shaped rhodium(I) core. In: Organometallics. 1996 ; Vol. 15, No. 7. pp. 1839-1844.
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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.

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