Mechanism of interaction between tertiary amines and trichlorosilane

Synthesis, isomer separation, and metal complexation studies of aza- and oxaphosphands, a class of hard/soft dinucleating phosphine macrocycles

“…3IP|IH| NMR chemical shifts were referenced in parts per million relative to external 85% H3P04. 13C{1 H| NMR spectra were referenced to the (15) Nomenclature: The phosphine coronands described here are assigned the name phosphand, modified to azaphosphand and oxaphosphand upon incorporation of metal-binding heteroatoms, N or O, within the macrocycle. For the azaphosphand two generic formulas are used.…”

“…Various macrocyclic ligands have been developed that provide the requisite subunits to form heterodinuclear complexes incorporating a soft, redox-active site and a hard, Lewis acid metal ion center.6 *** '10 Our studies of dinucleating macrocyclic ligands have focused on the coordination properties of homodinucleating hexaamine macrocycles11 and the chemistry of dicopper(I), dicopper(II), and dirhodium tropocoronand complexes.12 The latter has led to novel regiospecific enantioselective organocuprate-catalyzed conjugate addition of Grignard reagents to 2-cyclohexenone.13 **We have now developed a convenient synthetic method for preparing two new classes of phosphorus-containing heterodinucleating macrocycles, designated azaphosphand and oxaphosphand, respectively, exemplified by specific molecules [22]P202N3 and [21 ]P205. 14,15 (14) A preliminary account of part of this work is contained in: Wei, L.; Bell, A.; Warner, S.; Williams, I. D.; Lippard, S. J. J. Am.…”

Reactive Distillation-Aided Ultrapure Silane Production from Trichlorosilane: Process Simulation and Optimization

“…Within a normally operated RD column, the resin surfaces are mostly wetted by the liquid phase; thus, only the liquid phase reaction is considered, although the catalyst also behaves with activity for a gas phase reaction. A plausible mechanism indicates the disproportionation reactions are second order, and the net forward reaction rates for eqs 1−3 are 19,20…”

“…Within a normally operated RD column, the resin surfaces are mostly wetted by the liquid phase; thus, only the liquid phase reaction is considered, although the catalyst also behaves with activity for a gas phase reaction. A plausible mechanism indicates the disproportionation reactions are second order, and the net forward reaction rates for eqs – are , where x 0 , x 1 , x 2 , x 3 , and x 4 are the liquid-phase mole fractions of STC, TCS, DCS, MCS, and silane respectively; r is the reaction rate; k and K are the reaction rate constant and the chemical equilibrium constant, respectively, which can be expressed as where k 0 and K 0 are pre-exponential factors, E is the activation energy of forward reaction, and Δ H is the heat of reaction. For the present case, their values are regressed from experimental data as summarized in Table .…”

Cycloadditions. V. Stereoelectronic effects in the cycloaddition of dichloroketene to cyclohexenes

“…On the other hand, a most recent report by N. S. Isaacs and P. F. Stanbury, Chem. Commun., 1061(1970, indicates that ketene cycloaddition to 2-pentene is nonregioselective.…”