(tBu3SiO)2WCl4 | 1041477-60-4

• 英文名称: (tBu3SiO)2WCl4
• CAS: 1041477-60-4
• 化学式: C₂₄H₅₄Cl₄O₂Si₂W
• 分子量: 756.525
• InChiKey: GZIGBTWGXHDIEK-UHFFFAOYSA-J

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：

  (tBu3SiO)2WCl4 在 Na amalagam 作用下， 以 乙醚 为溶剂， 以95%的产率得到bis((tri-tert-butylsilyl)oxy)tungsten(V) chloride
  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：

  tri-tert-butylsilanol 、 六氯化钨 以 四氯化碳 为溶剂， 以90%的产率得到(tBu3SiO)2WCl4
  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

• Four-Coordinate Mo(II) as (silox)₂Mo(PMe₃)₂and Its W(IV) Congener (silox)₂HW(η²-CH₂PMe₂)(PMe₃) (silox =^<i>t</i>Bu₃SiO)
  作者：David S. Kuiper、Peter T. Wolczanski、Emil B. Lobkovsky、Thomas R. Cundari

  DOI：10.1021/ic8011958

  日期：2008.11.17

  The reduction of [((Bu3SiO)-Bu-t)(2)MOCl](2) (2(2)) provided the cyclometalated derivative, (silox)(2)HMoMo(kappa-O,C-OSi(t)Bu(2)CMe(2)Ch(2))(silox) (3), and alkylation of 2(2) with MeMgBr afforded [(tBu(3)SiO)(2)MoCH3](2) (4(2)). The hydrogenation of 4(2) was ineffective, but the reduction of 2(2) under H-2 generated [((Bu3SiO)-Bu-t)(2)MoH](2) (5(2)), and the addition of 2-butyne to 3 gave [(silox)(2)Mo](2)(mu:eta(2)eta(2)-C2Me2) (6), thereby implicating the existence of [(silox)(2)Mo](2) (1(2)). The addition of (silox)H to Mo(NMe2)(4) led to (silox)(2)Mo(NMe2)(2) (7), but further elaboration of the core proved ineffective. The silanolysis of MoCl5 afforded (silox)(2)MoCl4 (8) and (silox)(3)MoCl3 (9) as a mixture from which pure 8 could be isolated, and the addition of THF or PMe3 resulted in derivatives of 9 as (silox)(2)Cl3MoL (L = THF, 10; PMe3, 11). Reductions of 11 and (silox)(2)WCl4 (15) in the presence of excess PMe3 provided (silox)(2)Cl2MPMe3 (M = Mo, 12; W, 16) or (silox)(2)HW(eta(2)-CH2PMe2)PMe3 (14). While "(silox)(2)W(PMe3)(2)" was unstable with respect to W(N) as 14, a reduction of 12 led to the stable Mo(II) diphosphine, (silox)(2)Mo(PMe3)(2) (17). X-ray crystal structures of 10 (pseudo-O-h), 12 (square pyramidal), and 14 and 17 (distorted T-d) are reported. Calculations address the diamagnetism of 12 and 16, and the distortion of 17 and its stability to cyclometalation in contrast to 14.