69586-11-4Relevant academic research and scientific papers
Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes
Coles, Nathan T.,Gasperini, Danila,King, Andrew K.,Mahon, Mary F.,Webster, Ruth L.
, p. 6102 - 6112 (2020/07/21)
A detailed synthetic investigation into the dehydrocoupling of silanes with amines, phosphines, and alcohols using an iron precatalyst (1) is presented. We have furnished over 30 examples of aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N-H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed in depth. Beyond this we have explored the substrate scope of phosphinosilane formation which shows a preferential heterodehydrocoupling to give the phosphinosilane with primary and secondary silanes. Silylethers can also be prepared and alcohols that contain alkene functionality do not show any tendency to reduce the double bond.
Rh-catalyzed P-P bond activation
Geier, Stephen J.,Stephan, Douglas W.
, p. 99 - 101 (2008/09/20)
A Rh-catalyst derived from (NacNac)Rh(COE)(N2) effects the hydrogenation and silylation of P-P bonds to give secondary phosphines and silylphosphines, (Ph2PH) and (Ph2PSiRR′2) respectively; the latter process is shown to also involve the silylation of secondary phosphines. The Royal Society of Chemistry.
