(tBu3SiO)2Mo(PMe3)2 | 1078727-13-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (tBu3SiO)2Mo(PMe3)2
• 英文别名: molybdenum(2+);tritert-butyl(oxido)silane;trimethylphosphane
• CAS: 1078727-13-5
• 化学式: C₃₀H₇₂MoO₂P₂Si₂
• 分子量: 678.959
• InChiKey: VXQCIGMELUXZJD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (tBu3SiO)2MoCl2(PMe3) 、 三甲基膦 在 Na/Hg 作用下， 以 乙醚 为溶剂， 以68%的产率得到(tBu3SiO)2Mo(PMe3)2
  参考文献：
  名称：

  Four-Coordinate Mo(II) as (silox)₂Mo(PMe₃)₂and Its W(IV) Congener (silox)₂HW(η²-CH₂PMe₂)(PMe₃) (silox =^tBu₃SiO)

  摘要：

  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.

  DOI：

  10.1021/ic8011958