((t)Bu3SiO)3WCl | 353797-22-5

• 英文名称: ((t)Bu3SiO)3WCl
• CAS: 353797-22-5
• 化学式: C₃₆H₈₁ClO₃Si₃W
• 分子量: 865.597
• InChiKey: OJJPBYAPUTYFML-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  ((t)Bu3SiO)3WCl 以 乙醚 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Molybdenum and Tungsten Structural Differences are Dependent on nd_z²/(n + 1)s Mixing: Comparisons of (silox)₃MX/R (M = Mo, W; silox = ^tBu₃SiO)

  摘要：

  Treatment of trans-(Et2O)(2)MoCl4 with 2 or 3 equiv of Na(silox) (i.e., (NaOSiBu3)-Bu-t) afforded (Silox)(3)MoCl2 (1-Mo) or (silox)(3)MoCl (2-Mo). Purification of 2-Mo was accomplished via addition of PMe3 to precipitate (Silox)(3)CIMoPMe3 (2-MoPMe3), followed by thermolysis to remove phosphine. Use of MoCl3(THF)(3) with various amounts of Na(silox) produced (Silox)(2)ClMoMoCl(Silox)(2) (3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (Silox)(3)MoR (R = Me, 2-MoMe; Et, 2-MoEt). 2-MoEt was also synthesized from C2H4 and (Silox)(3)MoH, which was prepared from 2-Mo and NaBEt3H. Thermolysis of WCl6 with (HOSiBu3)-Bu-t afforded (Silox)(2)WCl4 (4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (Silox)(3)WCl2 (1-W, tbp, X-ray), which was alternatively prepared from trans-(Et2S)(2) WCl4 and 3 equiv of Tl(silox). Na/Hg reduction of 1-W generated (silox)(3)WCl (2-W). Alkylation of 2-W with MeMgBr produced (Silox)(3)WMe (2-WMe), which dehydrogenated to (Silox)(3)WCH (6-W) with Delta H-double dagger = 14.9(9) kcal/ mol and Delta S-double dagger = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-T-d (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/ molecular mechanics studies of the S = 0 and S = 1 states for full models of 2-Mo, 2-MoEt, 2-W and 2-WMe corroborate the experimental findings and are consistent with the greater nd(z)(2)/(n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.

  DOI：

  10.1021/ic800139c
• 作为产物：
  描述：

  在 Na amalagam 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到((t)Bu3SiO)3WCl
  参考文献：
  名称：

  Molybdenum and Tungsten Structural Differences are Dependent on nd_z²/(n + 1)s Mixing: Comparisons of (silox)₃MX/R (M = Mo, W; silox = ^tBu₃SiO)

  摘要：

  Treatment of trans-(Et2O)(2)MoCl4 with 2 or 3 equiv of Na(silox) (i.e., (NaOSiBu3)-Bu-t) afforded (Silox)(3)MoCl2 (1-Mo) or (silox)(3)MoCl (2-Mo). Purification of 2-Mo was accomplished via addition of PMe3 to precipitate (Silox)(3)CIMoPMe3 (2-MoPMe3), followed by thermolysis to remove phosphine. Use of MoCl3(THF)(3) with various amounts of Na(silox) produced (Silox)(2)ClMoMoCl(Silox)(2) (3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (Silox)(3)MoR (R = Me, 2-MoMe; Et, 2-MoEt). 2-MoEt was also synthesized from C2H4 and (Silox)(3)MoH, which was prepared from 2-Mo and NaBEt3H. Thermolysis of WCl6 with (HOSiBu3)-Bu-t afforded (Silox)(2)WCl4 (4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (Silox)(3)WCl2 (1-W, tbp, X-ray), which was alternatively prepared from trans-(Et2S)(2) WCl4 and 3 equiv of Tl(silox). Na/Hg reduction of 1-W generated (silox)(3)WCl (2-W). Alkylation of 2-W with MeMgBr produced (Silox)(3)WMe (2-WMe), which dehydrogenated to (Silox)(3)WCH (6-W) with Delta H-double dagger = 14.9(9) kcal/ mol and Delta S-double dagger = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-T-d (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/ molecular mechanics studies of the S = 0 and S = 1 states for full models of 2-Mo, 2-MoEt, 2-W and 2-WMe corroborate the experimental findings and are consistent with the greater nd(z)(2)/(n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.

  DOI：

  10.1021/ic800139c

文献信息

• Symmetry and Geometry Considerations of Atom Transfer:  Deoxygenation of (silox)₃WNO and R₃PO (R = Me, Ph, ^tBu) by (silox)₃M (M = V, NbL (L = PMe₃, 4-Picoline), Ta; silox = ^tBu₃SiO)
  作者：Adam S. Veige、LeGrande M. Slaughter、Emil B. Lobkovsky、Peter T. Wolczanski、Nikita Matsunaga、Stephen A. Decker、Thomas R. Cundari

  DOI：10.1021/ic0300114

  日期：2003.10.1

  Deoxygenations of (silox)(3)WNO (12) and R(3)PO (R = Me, Ph, (t)Bu) by M(silox)(3) (1-M; M = V, NbL (L = PMe(3), 4-picoline), Ta; silox = (t)Bu(3)SiO) reflect the consequences of electronic effects enforced by a limiting steric environment. 1-Ta rapidly deoxygenated R(3)PO (23 degrees C; R = Me (DeltaG degrees (rxn)(calcd) = -47 kcal/mol), Ph) but not (t)Bu(3)PO (85 degrees, >2 days), and cyclometalation

  （silox）（3）WNO（12）和R（3）PO（R = Me，Ph，（t）Bu）被M（silox）（3）（1-M; M = V，NbL（L = PMe（3），4-picoline），Ta; silox =（t）Bu（3）SiO）反映了有限空间环境所施加的电子效应的后果。1-Ta快速脱氧的R（3）PO（23摄氏度; R = Me（DeltaG摄氏度（rxn）（计算）= -47 kcal / mol），Ph），但没有（t）Bu（3）PO（85摄氏度） ，> 2天）和环金属化与12脱氧竞争为（silox）（3）WN（11）和（silox）（3）TaO（3-Ta; DeltaG度（rxn）（计算）= -100 kcal /摩尔）。1-V使12缓慢脱氧并与OPR（3）形成稳定的加合物（silox）（3）V-OPR（3）（3-OPR（3））。1-Nb（4-picoline）（S = 0）和1-NbPMe（3）（S