Kinetics of CO2 deinsertion from bis(phosphinite)ligated nickel and palladium pincer formate complexes have been investigated. Although the insertion of CO2 into the corresponding hydride complexes are thermodymamically favorable, the raction has been found to be reversible (figure 1). In order to understand the deinsertion process, reaction of metal formates has been studied in the presence of CS2 (figure 2). It is found that decarboxylation follows a pseudo frist order kinetics (rate = K[M-OCHO])at high concentration of CS2.The rate constant of CO2 deinsertion of these formate complexes with different substituents on phosphorous donors (tert-butyl and iso-propyl) have been measured at different temperatures. From the Eyring plots, the enthalpy and entropy of activation have also been calculated. Both the metal and phosphorous substituents have a significant impact on the rate of the process.

Kinetics of CO<sub>2 </sub>?deinsertion from bis(phosphinite)-ligated nickel and palladium pincer formate complexes

248th National Meeting (2014)

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Kinetics of CO2 ?deinsertion from bis(phosphinite)-ligated nickel and palladium pincer formate complexes

Kinetics of CO₂?deinsertion from bis(phosphinite)-ligated nickel and palladium pincer formate complexes