141997-35-5Relevant academic research and scientific papers
A bonding-reactivity relationship for Ni(PCy3)2(CO2): A comparative solid-state-solution nuclear magnetic resonance study (31P, 13C) as a diagnostic tool to determine the mode of bonding of CO2 to a metal center
Aresta, Michele,Gobetto, Roberto,Quaranta, Eugenio,Tommasi, Immacolata
, p. 4286 - 4290 (2008/10/08)
31P and 13C nuclear magnetic resonance spectra in the solid state and in solution, at variable temperature, have been used for the first time to determine a direct correlation of the modes of bonding of CO2 in Ni(PCy3)2(CO2) in the two states. In solution, at 173 K, CO2 is η2-CO bonded to nickel and 31P and 13C chemical shifts are almost identical with the value found for the solid complex, while a dynamic process averages, in solution, the two phosphorus atoms (ΔG? = 39.3 kJ mol-1) at room temperature through an intramolecular motion. The modification of the mode of bonding of CO2 to a metal center that occurs when a solid sample is dissolved in a solvent may be relevant to the reactivity of CO2-transition metal complexes, as shown by the reaction of coordinated CO2 with electrophiles (H+, Ag+) and H2. The temperature can play an important role.
