Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen) Complexes or Simple Metal Salts

The deuteration of a diverse group of silanes: alkyl‐, aryl‐, alkoxy‐ and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D 2 ) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes O(SiMe 2 H) 2 , Et 3 SiH, (EtO) 3 SiH and Me 2 ClSiH was possible with 0.1 mol% of the ruthenium complex [RuH 2 (η 2 ‐H 2 ) 2 (PCyp 3 ) 2 ] [0.05 mol% for O(SiMe 2 H) 2 ] when catalysis was conducted in the neat silane at 30 °C under 1 bar of D 2 for 3.5 h. The air‐stable ruthenium trichloride salt RuCl 3 ⋅x H 2 O was also an efficient catalyst for the deuteration of O(SiMe 2 H) 2 and Et 3 SiH; deuterium incorporations for the two silanes of 93% and 90%, respectively, were possible under the same conditions as for [RuH 2 (η 2 ‐H 2 ) 2 (PCyp 3 ) 2 ] with 0.1% catalyst loading. Hydrogen–deuterium exchange of O(SiMe 2 H) 2 catalyzed by the rhodium trichloride (RhCl 3 ⋅x H 2 O) and iridium trichloride (IrCl 3 ⋅x H 2 O) was similarly efficient as with RuCl 3 ⋅x H 2 O although catalytic alacrity dropped for Et 3 SiH.