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

<jats:title>Abstract</jats:title><jats:p>The deuteration of a diverse group of silanes: alkyl‐, aryl‐, alkoxy‐ and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D<jats:sub>2</jats:sub>) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes O(SiMe<jats:sub>2</jats:sub>H)<jats:sub>2</jats:sub>, Et<jats:sub>3</jats:sub>SiH, (EtO)<jats:sub>3</jats:sub>SiH and Me<jats:sub>2</jats:sub>ClSiH was possible with 0.1 mol% of the ruthenium complex [RuH<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐H<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>(PCyp<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] [0.05 mol% for O(SiMe<jats:sub>2</jats:sub>H)<jats:sub>2</jats:sub>] when catalysis was conducted in the neat silane at 30 °C under 1 bar of D<jats:sub>2</jats:sub> for 3.5 h. The air‐stable ruthenium trichloride salt RuCl<jats:sub>3</jats:sub>⋅x H<jats:sub>2</jats:sub>O was also an efficient catalyst for the deuteration of O(SiMe<jats:sub>2</jats:sub>H)<jats:sub>2</jats:sub> and Et<jats:sub>3</jats:sub>SiH; deuterium incorporations for the two silanes of 93% and 90%, respectively, were possible under the same conditions as for [RuH<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐H<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>(PCyp<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] with 0.1% catalyst loading. Hydrogen–deuterium exchange of O(SiMe<jats:sub>2</jats:sub>H)<jats:sub>2</jats:sub> catalyzed by the rhodium trichloride (RhCl<jats:sub>3</jats:sub>⋅x H<jats:sub>2</jats:sub>O) and iridium trichloride (IrCl<jats:sub>3</jats:sub>⋅x H<jats:sub>2</jats:sub>O) was similarly efficient as with RuCl<jats:sub>3</jats:sub>⋅x H<jats:sub>2</jats:sub>O although catalytic alacrity dropped for Et<jats:sub>3</jats:sub>SiH.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/gif" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/mcontent.gif"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text></jats:p>