Complexation of N2, H2, CO2, and Ethylene to a T-Shaped Rhodium(I) Core

摘要: 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 various small gaseous molecules, giving rise to complexes Rh(X)[HC(CH2CH2P(t-Bu)2)2], X = H2 (3), C2H4 (4), CO2 (5). first 16 electron rhodium−carbon dioxide 5 is spectroscopically characterized. All transformations are reversible in presence free nitrogen. thermodynamic parameters for these equilibria reactions have been evaluated. It found that at 25 °C formation dihydrogen 3 about 1.24 kcal/mol more favorable than its dinitrogen analogue 2, whereas carbon (5) and, surprisingly, ethylene (4) less 2.97 and 1.57 kcal/mol, respectively, yielding ligating ability Rh(I) T-shaped core L > N2 (CO2). formate HRh(O2CH)[HC(CH2CH2P(t-Bu)2)2] (7) can...