197173-79-8

Upstream product

• 154030-85-0 Ti(Me)(OSi-t-Bu₃)2(NHSi-t-Bu₃) 
• 71-43-2 benzene 
• 197173-75-4 (tri-tert-butylsilylamido)bis(tri-tert-butylsilyloxy)(cyclopentyl)titanium 
• 1076-43-3 benzene-d6 
• 137917-77-2 Ti(OSi(C(CH₃)3)3)2Cl₂ 
• 97733-16-9 Na(silox) 
• 154030-84-9 (NHSi(C(CH₃)3)3)(OSi(C(CH₃)3)3)2TiCl 

Downstream Products

• 154030-87-2 Ti(benzyl)(OSi-t-Bu₃)2(NHSi-t-Bu₃) 

Relevant academic research and scientific papers

Inter- and intramolecular experimental and calculated equilibrium isotope effects for (silox)2((t)Bu3SiND)TiR + RH (silox = (t)Bu3SiO): Inferred kinetic isotope effects for RH/D addition to transient (silox)2Ti

Intermolecular equilibrium isotope effects (EIEs) were measured (26.5 °C) and calculated for (silox)2((t)Bu3SiND)TiR(D) (1-ND-R(D)) + R(H)H ? (silox)2((t)Bu3SiNH)TiR(H) (1-R(H)) + R(D)D: R(H)H/R(D)D = CH4/

Selectivities in hydrocarbon activation: Kinetic and thermodynamic investigations of reversible 1,2-RH-elimination from (silox)2((t)Bu3SiNH)TiR (silox = (t)Bu3SiO)

Addition of 2.0 equiv of Na(silox) to TiCl4(THF)2 afforded (silox)2TiCl2 (1), which yielded (silox)2-((t)Bu3SiNH)TiCl (2-Cl) upon treatment with (t)Bu3SiNLi. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)2Ti=NSi(t)Bu3 (3) produced (silox)2((t)Bu3SiNH)TiR (2-R; R = Me, Et, CH2Ph = Bz, CH=CH2 = Vy, (c)Bu, (n)Bu, Ph, H, (c)Pr, (c)Pe, CH2-3,5-Me2C6H3 = Mes, (neo)Hex, (c)Hex, η3-H2CHCH2, η3-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and HC2(t)Bu into the titanium-hydride bond of 2-H generated (silox)2((t)Bu3SiNH)TiR (2-R; R = Et, η3-H2CCHCHMe, Vy, E-CH=CH(t)Bu). Trapping of 3 by donors L afforded (silox)2LTi=NSi(t)Bu3 (3-L; L = OEt2, THF (X-ray, two independent molecules: d(Ti=N) = 1.772(3), 1.783(3) A?) py, PMe3, NMe3, NEt3) and metallacycles (silox)2((t)Bu3SiN)TiCR=CR' (3-RC2R'; RC2R' = HC2H MeC2Me, EtC2Et, HC2(t)Bu) and (silox)2((t)Bu3SiN)TiCH2CH2 (3-C2H4) Kinetics of 1,2-RH-elimination from 2-R revealed a fist-order process (24.8 °C): R = Bz -5 s-1) 2-(c)Pe > 2-(n)Pr ~ 2-(n)Bu > 2-(neo)Hex > 2-Et > 2-(c)Bu > 2-CH2SiMe3 > 2-Ph > 2-Me > 2-Bz > 2-(c)Pr ~ 2-Mes > 2-Vy > 3-C2H4 > 3-NEt3 > 2-H > 3-OEt2 > 3-EtC2Et > 3-MeC2Me > 3-THF > 3-NMe3 > 3-PMe3 > 3-py. A correlation of D(TiR)(rel) to D(RH) revealed greater differences in titanium-carbon bond energies. THF loss from 3-THF allowed a rough estimate of ΔG°(3). Using thermochemical cycles, relative activation energies for 1,2-RH-addition were assessed: (c)HexH > (c)PeH > (n)BuH > (neo)HexH > EtH > BzH > (c)BuH > MesH > MeH > PhH > (c)PrH > VyH > 3-C2H4 formation > H2. On the basis of a parabolic model, C-H bond activation selectivities are influenced by the relative ground state energies of 2-R and a:parameter representing the reaction coordinate, A more compressed reaction coordinate for sp2- vs sp3-substrates eases their activation.