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Upstream product

• 816-43-3 lithium diethylamide 
• 789-25-3 HSiPh₃ 
• 109-89-7 diethylamine 

Relevant academic research and scientific papers

Alkali-Metal-Catalyzed Cross-Dehydrogenative Couplings of Hydrosilanes with Amines

We report the N-H/H-Si cross-dehydrogenative coupling (CDC) of hydrosilanes and amines with high conversion (>90 %) and chemoselectivity for the production of silazanes, using group 1 metal hexamethyldisilazides [MN(SiMe3)2] (M=Li, Na, K) as precatalysts under mild conditions. [KN(SiMe3)2] showed higher activity than the congeneric lithium and sodium salts. The catalyzed CDC reaction displays a broad substrate scope. Phenylsilane and diphenylsilane react with a number of amines under ambient conditions; more elevated temperature is required for triphenylsilane to undergo CDC reactions. The intermediate lithium complex [(THF)2Li-{N(SiHPh2)(Dipp)}] (1) has been isolated and characterized in an attempt to identify the operative reaction mechanism.

Hetero-dehydrocoupling of silanes and amines by heavier alkaline earth catalysis

The homoleptic alkaline earth hexamethyldisilazides, [M{N(SiMe 3)2}2]2 (1: M = Mg; 2: M = Ca; 3: M = Sr), have been demonstrated as active pre-catalysts for the cross-dehydrocoupling of Si-H and N-H bonds under mild (25-60 °C) conditions. The reactions are applicable to the coupling of a wide variety of amine and silane substrates and are proposed to occur via a sequence of discrete Si-H/M-N and N-H/M-H metathesis steps. Whereas reactions of dialkyl group 2 species with 2,6-di-iso-propylaniline and phenylsilane delivered a series of well-defined compounds consistent with this rationale, kinetic analysis of the cross-coupling of diethylamine with diphenylsilane provided evidence for a more complex and subtly variable mechanistic landscape. Although reactions performed with all three pre-catalysts presented a number of common features, in every case the calcium species, 2, was found to provide notably superior catalytic activity, an order of magnitude higher than both 1 and 3 and in excess of many previously described benchmark transition metal- or f-element-mediated processes. Variations in overall reaction order, mode of pre-catalyst activation and the nature of the rate determining process are postulated to arise as a consequence of the marked change in M2+ radius and resultant charge density as group 2 is descended. The Royal Society of Chemistry 2013.

Photolysis of Diethyl(triphenylmethyl)amine and Diethyl(triphenylsilyl)amine

Upon UV irradiation, diethyl(triphenylmethyl)amine or diethyl(triphenylsilyl)amine underwent a homolytic C-N or Si-N bond cleavage to give triphenylmethyl or triphenylsilyl radicals, which abstracted a hydrogen atom from the solvent to give triphenylmetha