Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen) Complexes or Simple Metal Salts. Issue 4 (20th February 2014)

• Record Type: Journal Article
• Authors: Smart, Katharine A.; Mothes‐Martin, Emmanuelle; Annaka, Tatsuro; Grellier, Mary; Sabo‐Etienne, Sylviane
• Is Part Of: Advanced synthesis & catalysis. Volume 356:Issue 4(2014)
• Page Start: 759
• Page End: 764
• Publication Date: 2014-02-20
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201300902
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The deuteration of a diverse group of silanes: alkyl‐, aryl‐, alkoxy‐ and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D<sub>2</sub>) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes O(SiMe<sub>2</sub>H)<sub>2</sub>, Et<sub>3</sub>SiH, (EtO)<sub>3</sub>SiH and Me<sub>2</sub>ClSiH was possible with 0.1 mol% of the ruthenium complex [RuH<sub>2</sub>(η<sup>2</sup>‐H<sub>2</sub>)<sub>2</sub>(PCyp<sub>3</sub>)<sub>2</sub>] [0.05 mol% for O(SiMe<sub>2</sub>H)<sub>2</sub>] when catalysis was conducted in the neat silane at 30 °C under 1 bar of D<sub>2</sub> for 3.5 h. The air‐stable ruthenium trichloride salt RuCl<sub>3</sub>⋅x H<sub>2</sub>O was also an efficient catalyst for the deuteration of O(SiMe<sub>2</sub>H)<sub>2</sub> and Et<sub>3</sub>SiH; deuterium incorporations for the two silanes of 93% and 90%, respectively, were possible under the same conditions as for [RuH<sub>2</sub>(η<sup>2</sup>‐H<sub>2</sub>)<sub>2</sub>(PCyp<sub>3</sub>)<sub>2</sub>] with 0.1% catalyst loading. Hydrogen–deuterium exchange of O(SiMe<sub>2</sub>H)<sub>2</sub> catalyzed by the rhodium trichloride (RhCl<sub>3</sub>⋅x H<sub>2</sub>O) and iridium trichloride (IrCl<sub>3</sub>⋅x H<sub>2</sub>O) was similarly efficient as with RuCl<sub>3</sub>⋅x H<sub>2</sub>O although catalytic alacrity dropped for Et<sub>3</sub>SiH.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg4sx5zxt7" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>