A new catalytic route for the formation of arene−silicon bonds based on the transfer dehydrogenative coupling of triethylsilane with an arene (Ar−X:  X = −CF3, −F, −H, −CH3, −Cl, −Br) in the presence of 3,3-dimethylbut-1-ene (tBu-ethylene) is reported. Rhodium and ruthenium catalysts (η5-C5Me5)Rh(H)2(SiEt3)2 and (η6-arene)Ru(H)2(SiEt3)2 and their corresponding dimeric chloride precursors not only catalyze the coupling of Et3SiH with an arene but additionally promote the dimerization of Et3SiH producing a carbosilane, Et3Si−CHMe−SiEt2H.