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A pathway for the catalytic hydrosilylation of carbonyl substrates with M(C 6 F 5 ) 3 (M = B, Al and Ga) was calculated by DFT (B3PW91-D3) and it was shown that in the case of the Al reagent, the carbonyl substrate binds irreversibly and inhibits catalysis by generating a stable carbonyl adduct. In contrast, the reduced electrophilicity of B(C 6 F 5 ) 3 disfavors the binding of the carbonyl substrate and increases the concentration of an activated silane adduct which is the species responsible for catalytic turnover. A similar mechanism was found for both cationic and neutral Re( iii ) species. Further, it was shown by tuning the electrophilicity of the rhenium catalysts, conditions can be found that would enable the catalytic hydrosilylation of ketone and nitrile substrates that were unreactive in previously reported systems. Thus the mechanisms proposed in this work, lay the foundation for the design of new catalytic systems. 

Cp*Ir( iii ) complexes have been shown to be effective for the halogenation of N , N -diisopropylbenzamides with N -halosuccinimide as a suitable halogen source. The optimized conditions for the iodination reaction consist of 0.5 mol% [Cp*IrCl 2 ] 2 in 1,2-dichloroethane at 60 °C for 1 h to form a variety of iodinated benzamides in high yields. Increasing the catalyst loading to 6 mol% and the time to 4 h enabled the bromination reaction of the same substrates. Reactivity was not observed for the chlorination of these substrates. A variety of functional groups on the para -position of the benzamide were well tolerated. Kinetic studies showed the reaction dependence is first order in iridium, positive order in benzamide, and zero order in N -iodosuccinimide. A KIE of 2.5 was obtained from an independent H/D kinetic isotope effect study. Computational studies (DFT-BP3PW91) indicate that a CMD mechanism is more likely than an oxidative addition pathway for the C–H bond activation step. The calculated functionalization step involves an Ir( v ) species that is the result of oxidative addition of acetate hypoiodite that is generated in situ from N -iodosuccinimide and acetic acid.