A theoretical investigation of the ChalkHarrod and modified ChalkHarrod mechanisms involved in hybrid integrated circuit building ?
Nowadays the relevance of silicon chemistry is spreading due to the applications of Si, in particular in semiconductors, in order to obtain an increasing number of performing materials. A theoretical investigation based on the Density Functional Theory has been done on the reaction paths implied in the Pt-catalysed alkene hydrosilylation, a process through which the selective grafting of organic molecules to silicon can be obtained. We studied the Si?H oxidative addition of SiH4 to a diphosphine molecule, the C2H4 insertion on Pt?H and Pt?SiH3 bonds, the isomerisation of the product of the C2H4 insertion, and the two following Si?C and C?H reductive eliminations. The set of these processes are known as the ChalkHarrod mechanism and the modified ChalkHarrod mechanism, respectively. The main goal of this work has been to identify the rate determining step of both mechanisms. Moreover, by employing dynamics simulations, we have reached a possible alternative product in the oxidative addition step.
chalkharrod mechanism density functional theory oxidative addition rate determining step car-parrinello molecular dynamics