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

Abstract

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 OA C H T U N G T R E N N U N G (SiMe 2 H) 2 , Et 3 SiH, (EtO) 3 SiH and Me 2 ClSiH was possible with 0.

Exhaustive Reduction of Esters Enabled by Nickel Catalysis

“…In contrast, the use of NiBr2•glyme/TMDSO/Mn in toluene-d8 resulted in an efficient 73% yield with >95%D incorporation (Scheme 4a). This procedure was found to be general, enabling the synthesis of several -CD3-containing molecules in good yield and high deuterium incorporation (41)(42)(43). Experiments in non-deuterated toluene gave ~5-10% reduced deuterium incorporation.…”

“…In order to transform TMDSO into its deuterated analog, a modified literature procedure was used. 41 Inside of a nitrogen-filled glovebox, 10 mg RuCl3•H2O is crushed into a fine powder and added alongside 3.0 mL of TMDSO to a 25 mL heavy-walled vacuum Schlenk tube. The tube is connected to a Buchi "tinyclave" pressure reactor and sealed.…”

“…This cycle (pressurize vessel, stir, freeze-pump-thaw) was repeated 6 times until analysis of an aliquot by 1 H NMR showed >95% deuterium incorporation. The spectroscopically pure d2-TMDSO (61% yield) can be purified by distillation to remove remaining RuCl3; 41 however, this was not found to be necessary. The crude material was thus used in subsequent reduction reactions without further purification as a black, translucent liquid.…”

Société Chimique de France 2014 Prize Winners

“…Sabo‐Etienne’s research involves coordination chemistry, organometallic chemistry, and catalysis. She has reported in Advanced Synthesis & Catalysis on silane deuteration,6a and in Angewandte Chemie on BH, CH, and BC activation 6b …”

Preise der Société Chimique de France 2014

“…Ihre Forschungsthemen sind die Koordinationschemie, die Organometallchemie und die Katalyse. Sie hat in Advanced Synthesis & Catalysis über die Deuterierung von Silanen6a und in der Angewandten Chemie über die B‐H‐, C‐H‐ und B‐C‐Aktivierung berichtet 6b …”