Ti(Ph)(OSi-t-Bu3)2(NHSi-t-Bu3) | 197173-79-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ti(Ph)(OSi-t-Bu3)2(NHSi-t-Bu3)
• CAS: 197173-79-8
• 化学式: C₄₂H₈₇NO₂Si₃Ti
• 分子量: 770.295
• InChiKey: NKKJLUXAKGZITC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.25
• 重原子数：
  49
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  47.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ti(Ph)(OSi-t-Bu3)2(NHSi-t-Bu3) 以 环己烷 为溶剂， 生成
  参考文献：
  名称：

  Selectivities in Hydrocarbon Activation:  Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)₂(^tBu₃SiNH)TiR (silox = ^tBu₃SiO)

  摘要：

  Addition of 2.0 equiv of Na(silox) to TiCl4(THF)(2) afforded (silox)(2)TiCl2 (1), which yielded (silox)(2)((Bu3SiNH)-Bu-t)TiCl (2-Cl) upon treatment with (Bu3SiNLi)-Bu-t. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)(2)Ti=(NSiBu3)-Bu-t (3) produced (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Me, Et, CH2Ph = Bz, CH=CH2 = Vy, Bu-c, Bu-n, Ph, H, Pr-c, (c)Pe, CH2-3,5-Me2C6H3 = Mes, (neo)Hex, (c)Hex, eta(3)-H2CHCH2, eta(3)-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and (HC2Bu)-Bu-t into the titanium-hydride bond of 2-H generated (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Et, eta(3)-H2CCHCHMe, Vy, E-CH=(CHBu)-Bu-t). Trapping of 3 by donors L afforded (silox)(2)LTi=(NSiBu3)-Bu-t (3-L; L = OEt2, THF (X-ray, two independent molecules: d(Ti=N) = 1.772(3), 1.783(3) Angstrom), py, PMe3, NMe3, NEt3) and metallacycles (silox)(2)((Bu3SiN)-Bu-t)TiCR=CR' (3-RC2R'; RC2R' = HC2H, MeC2Me, EtC2Et, (HC2Bu)-Bu-t) and (silox)(2)((Bu3SiN)-Bu-t)TiCH2CH2 (3-C2H4). Kinetics of 1,2-RH-elimination from 2-R revealed a first-order process (24.8 degrees C): R = Bz < Mes < H < Me (1.54(10) x 10(-5) s(-1)) < (neo)Hex < Et < Bu-n < Bu-c < (c)Pe < (c)Hex < Pr-c < Vy < Ph. Kinetics data, large 1,2-RH/D-elimination KIE's (e.g., MeH/D, 13.7(9), 24.8 degrees C), and Eyring parameters (e.g., 2-Me, Delta H double dagger = 20.2(12) kcal/mol, Delta S double dagger = -12(4) eu) portray a four-center, concerted transition state when the N ... H ... R linkage is nearly linear. Equilibrium measurements led to the following relative standard free energy scale: 2-(c)Hex > 2-(c)Pe > 2-Pr-n similar to 2-Bu-n > 2-(neo)Hex > 2-Et, 2-Bu-c > 2-CH2SiMe3 > 2-Ph > 2-Me > 2-Bz > 2-Pr-c similar to 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 Delta G degrees(3). Using thermochemical cycles, relative activation energies for 1,2-RH-addition were assessed: (c)HexH > (c)PeH > (BuH)-Bu-n > (neo)HexH > EtH > BzH > (BuH)-Bu-c > MesH > MeH > PhH > (PrH)-Pr-c > VyH > 3-C2H4 formation > H-2. 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 sp(2)- vs sp(3)-substrates eases their activation.

  DOI：

  10.1021/ja9707419
• 作为产物：
  描述：

  Na(silox) 以 乙醚 、 苯 为溶剂， 生成 Ti(Ph)(OSi-t-Bu3)2(NHSi-t-Bu3)
  参考文献：
  名称：

  Selectivities in Hydrocarbon Activation:  Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)₂(^tBu₃SiNH)TiR (silox = ^tBu₃SiO)

  摘要：

  Addition of 2.0 equiv of Na(silox) to TiCl4(THF)(2) afforded (silox)(2)TiCl2 (1), which yielded (silox)(2)((Bu3SiNH)-Bu-t)TiCl (2-Cl) upon treatment with (Bu3SiNLi)-Bu-t. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)(2)Ti=(NSiBu3)-Bu-t (3) produced (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Me, Et, CH2Ph = Bz, CH=CH2 = Vy, Bu-c, Bu-n, Ph, H, Pr-c, (c)Pe, CH2-3,5-Me2C6H3 = Mes, (neo)Hex, (c)Hex, eta(3)-H2CHCH2, eta(3)-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and (HC2Bu)-Bu-t into the titanium-hydride bond of 2-H generated (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Et, eta(3)-H2CCHCHMe, Vy, E-CH=(CHBu)-Bu-t). Trapping of 3 by donors L afforded (silox)(2)LTi=(NSiBu3)-Bu-t (3-L; L = OEt2, THF (X-ray, two independent molecules: d(Ti=N) = 1.772(3), 1.783(3) Angstrom), py, PMe3, NMe3, NEt3) and metallacycles (silox)(2)((Bu3SiN)-Bu-t)TiCR=CR' (3-RC2R'; RC2R' = HC2H, MeC2Me, EtC2Et, (HC2Bu)-Bu-t) and (silox)(2)((Bu3SiN)-Bu-t)TiCH2CH2 (3-C2H4). Kinetics of 1,2-RH-elimination from 2-R revealed a first-order process (24.8 degrees C): R = Bz < Mes < H < Me (1.54(10) x 10(-5) s(-1)) < (neo)Hex < Et < Bu-n < Bu-c < (c)Pe < (c)Hex < Pr-c < Vy < Ph. Kinetics data, large 1,2-RH/D-elimination KIE's (e.g., MeH/D, 13.7(9), 24.8 degrees C), and Eyring parameters (e.g., 2-Me, Delta H double dagger = 20.2(12) kcal/mol, Delta S double dagger = -12(4) eu) portray a four-center, concerted transition state when the N ... H ... R linkage is nearly linear. Equilibrium measurements led to the following relative standard free energy scale: 2-(c)Hex > 2-(c)Pe > 2-Pr-n similar to 2-Bu-n > 2-(neo)Hex > 2-Et, 2-Bu-c > 2-CH2SiMe3 > 2-Ph > 2-Me > 2-Bz > 2-Pr-c similar to 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 Delta G degrees(3). Using thermochemical cycles, relative activation energies for 1,2-RH-addition were assessed: (c)HexH > (c)PeH > (BuH)-Bu-n > (neo)HexH > EtH > BzH > (BuH)-Bu-c > MesH > MeH > PhH > (PrH)-Pr-c > VyH > 3-C2H4 formation > H-2. 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 sp(2)- vs sp(3)-substrates eases their activation.

  DOI：

  10.1021/ja9707419

文献信息

• Inter- and Intramolecular Experimental and Calculated Equilibrium Isotope Effects for (silox)₂(^tBu₃SiND)TiR + RH (silox = ^tBu₃SiO):  Inferred Kinetic Isotope Effects for RH/D Addition to Transient (silox)₂TiNSi^tBu₃
  作者：LeGrande M. Slaughter、Peter T. Wolczanski、Thomas R. Klinckman、Thomas R. Cundari

  DOI：10.1021/ja000112q

  日期：2000.8.23

  This article discusses inter- and intramolecular experimental and calculated equilibrium isotope effects.

  本文讨论了分子间和分子内实验和计算的平衡同位素效应。
• Energetics of C-H Bond Activation and Ethylene Binding to d0 Transient (silox)2Ti:NSitBu3
  作者：Jordan L. Bennett、Peter T. Wolczanski

  DOI：10.1021/ja00084a082

  日期：1994.3
• Selectivities in Hydrocarbon Activation:  Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)₂(^tBu₃SiNH)TiR (silox = ^tBu₃SiO)
  作者：Jordan L. Bennett、Peter T. Wolczanski

  DOI：10.1021/ja9707419

  日期：1997.11.1

  Addition of 2.0 equiv of Na(silox) to TiCl4(THF)(2) afforded (silox)(2)TiCl2 (1), which yielded (silox)(2)((Bu3SiNH)-Bu-t)TiCl (2-Cl) upon treatment with (Bu3SiNLi)-Bu-t. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)(2)Ti=(NSiBu3)-Bu-t (3) produced (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Me, Et, CH2Ph = Bz, CH=CH2 = Vy, Bu-c, Bu-n, Ph, H, Pr-c, (c)Pe, CH2-3,5-Me2C6H3 = Mes, (neo)Hex, (c)Hex, eta(3)-H2CHCH2, eta(3)-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and (HC2Bu)-Bu-t into the titanium-hydride bond of 2-H generated (silox)(2)((Bu3SiNH)-Bu-t)TiR (2-R; R = Et, eta(3)-H2CCHCHMe, Vy, E-CH=(CHBu)-Bu-t). Trapping of 3 by donors L afforded (silox)(2)LTi=(NSiBu3)-Bu-t (3-L; L = OEt2, THF (X-ray, two independent molecules: d(Ti=N) = 1.772(3), 1.783(3) Angstrom), py, PMe3, NMe3, NEt3) and metallacycles (silox)(2)((Bu3SiN)-Bu-t)TiCR=CR' (3-RC2R'; RC2R' = HC2H, MeC2Me, EtC2Et, (HC2Bu)-Bu-t) and (silox)(2)((Bu3SiN)-Bu-t)TiCH2CH2 (3-C2H4). Kinetics of 1,2-RH-elimination from 2-R revealed a first-order process (24.8 degrees C): R = Bz < Mes < H < Me (1.54(10) x 10(-5) s(-1)) < (neo)Hex < Et < Bu-n < Bu-c < (c)Pe < (c)Hex < Pr-c < Vy < Ph. Kinetics data, large 1,2-RH/D-elimination KIE's (e.g., MeH/D, 13.7(9), 24.8 degrees C), and Eyring parameters (e.g., 2-Me, Delta H double dagger = 20.2(12) kcal/mol, Delta S double dagger = -12(4) eu) portray a four-center, concerted transition state when the N ... H ... R linkage is nearly linear. Equilibrium measurements led to the following relative standard free energy scale: 2-(c)Hex > 2-(c)Pe > 2-Pr-n similar to 2-Bu-n > 2-(neo)Hex > 2-Et, 2-Bu-c > 2-CH2SiMe3 > 2-Ph > 2-Me > 2-Bz > 2-Pr-c similar to 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 Delta G degrees(3). Using thermochemical cycles, relative activation energies for 1,2-RH-addition were assessed: (c)HexH > (c)PeH > (BuH)-Bu-n > (neo)HexH > EtH > BzH > (BuH)-Bu-c > MesH > MeH > PhH > (PrH)-Pr-c > VyH > 3-C2H4 formation > H-2. 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 sp(2)- vs sp(3)-substrates eases their activation.