To gain further insight, we performed DFT calculations (Figure ), whereby IiPr (L) was employed instead of ICy to reduce calculation costs. The reaction is initiated by the replacement of 1,4-cyclooctadiene (cod) of [(L2Ni)2cod] with 1a to form arene complex A, which is energetically slightly favored. We then examined two possible scenarios: (1) dissociation of a ligand from A followed by oxidative addition and transmetalation with the hydrosilane, and (2) oxidative addition followed by ligand exchange between L and hydrosilane. The dissociation of free L from A is energetically unfavorable by +17.9 kcal/mol. Furthermore, the oxidative addition of a C-F bond to give η 3 -benzyl complex C requires +41.5 kcal/mol. Importantly, the relatively high TS barrier for TS1 is inconsistent with the experimental results. In contrast, the oxidative addition of A to give Ni fluoride complex D requires only +20.7 kcal/mol and is thus thermodynamically more favorable. The dissociation of L from D followed by the coordination of hydrosilane is energetically unfavorable, albeit that the subsequent transmetalation with hydrosilane is a thermodynamically favorable process due to the formation of a stable Si-F bond. The reductive elimination of complex G to give complex H can be expected to be fast according to the calculated TS energy.