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• 123-75-1 pyrrolidine 
• 775-12-2 diphenylsilane 

Relevant academic research and scientific papers

Syntheses of Dianionic α-Iminopyridine Rare-Earth Metal Complexes and Their Catalytic Acitivities toward Dehydrogenative Coupling of Amines with Hydrosilanes

Reactions of [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 with aminomethylene-substituted pyridine 2-[O(CH2CH2)2NCH2CH2NCH2]C5H4N (1) gave the dianionic α-iminopyridine rare-earth metal amido complexes {μ-η2:σ1:κ1:κ1-2-[O(CH2CH2)2NCH2CH2NCH]C5H4N}2RE2[N(SiMe3)2]2 (RE = Y(2a), La(2b), Pr(2c), Nd(2d), Sm(2e), Dy(2f), Er(2g), and Lu (2h)). However, reaction of [(Me3Si)2N]3Y(μ-Cl)Li(THF)3 with pyridin-2-ylmethyl-substituted amines such as 2-(RNHCH2)C5H4N (R = tBu (3a) and 2,6-iPr2Ph (3b)) or benzyl-substituted amine O(CH2CH2)2NCH2CH2NHCH2C6H5 (5) afforded the corresponding yttrium complexes containing monoanionic ligands [2-(RNCH2)C5H4N]2YN(SiMe3)2 (R = tBu (4a) and 2,6-iPr2Ph (4b)) or [O(CH2CH2)2NCH2CH2NCH2C6H5][(Me3Si)2N)]Y(μ-Cl)(μ-η3-O(CH2CH2)2NCH2CH2NCH2C6H5)Li(THF) (6). Dianionic α-iminopyridine rare-earth metal amido complexes showed high catalytic activities for the dehydrogenation coupling reaction of hydrosilanes and amines providing a variety of silylamines in high yields.

Reactivity of [TismPriBenz]MgMe towards secondary amines and terminal alkynes: Catalytic dehydrocoupling with hydrosilanes to afford Si–N and Si–C bonds

The magnesium hydride and methyl compounds, [TismPriBenz]MgX (X = H, Me), react with diphenylamine (Ph2NH)and pyrrolidine (C4H8NH)to afford the amide derivatives, [TismPriBenz]MgNPh2 and [TismPriBenz]MgNC4H8, while reactions with the terminal alkynes, PhC[tbnd]CH and BunC[tbnd]CH, afford the corresponding acetylide derivatives, [TismPriBenz]MgC[tbnd]CPh and [TismPriBenz]MgC[tbnd]CBun. The Mg[sbnd]N bond of [TismPriBenz]MgNR2 may be cleaved by hydrosilanes, such that [TismPriBenz]MgMe is an effective precatalyst for the dehydrocoupling of hydrosilanes and amines. For example, [TismPriBenz]MgMe enables the conversion of a 1:1 mixture of Ph2SiH2 and C4H8NH at room temperature to the silazane, Ph2SiH(NC4H8). [TismPriBenz]MgH and [TismPriBenz]MgMe are also capable of dehydrocoupling PhC[tbnd]CH and PhSiH3 to form PhSiH2C[tbnd]CPh. In addition to dehydrocoupling of terminal alkynes, [TismPriBenz]MgMe is also capable of achieving the isomerization 3-phenyl-1-propyne to phenylallene.

Selective catalytic synthesis of amino-silanes at part-per million catalyst loadings

Platinum(ii) complex [Pt(ItBu′)(ItBu)][BArF4] (1a) is a highly active and selective catalyst in the dehydrocoupling of amines and silanes at part-per-million catalyst loadings (up to 10 ppm, 0.001 mol%), achievi

Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism

Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3SiH with pyrrolidine or tBuNH2. Ae{

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.