A catalytic synthesis of deuterated silanes SiEt3D, SiMe2PhD and SiPh2D2 is reported that allows their facile generation in a 3–4 g scale, utilizing D2 (0.5 bar) as the hydrogen isotope source and low catalyst loadings (0.01 mol%). The catalyst precursor is the rhodium (III) complex 1, which contains a (η5-C5Me5)Rh cation stabilized by coordination to a cyclometallated phoshine PMeXyl2 (Xyl = 2,6-C6H3Me2). The same complex is also an active catalyst for the hydrosilylation of the CO and C≡N bonds of various ketones, aldehydes and α,β-unsaturated nitriles. Hence, combination of these two properties permits development of a simple and proficient one-flask, two-step procedure for the deuterosilylation of these substrates. Copyright © 2011 John Wiley & Sons, Ltd.