N-Trimethylsilyl-tri-n-butyl-phosphinimin | 17921-92-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N-Trimethylsilyl-tri-n-butyl-phosphinimin
• 英文别名: Tributyl[(trimethylsilyl)imino]-lambda~5~-phosphane；tributyl(trimethylsilylimino)-λ5-phosphane
• CAS: 17921-92-5
• 化学式: C₁₅H₃₆NPSi
• 分子量: 289.517
• InChiKey: IXRVYDSESGAYGZ-UHFFFAOYSA-N

物化性质

• 沸点：
  94 °C(Press: 0.1 Torr)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.42
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-Trimethylsilyl-tri-n-butyl-phosphinimin 以 甲醇 为溶剂， 反应 16.0h， 以85%的产率得到三正丁基氧化磷
  参考文献：
  名称：

  Syntheses and reactions of the bis-boryloxide O(Bpin)2(pin = O2C2Me4)

  摘要：

  磷烯氧化物OPEt3和OPn-Bu3与pinacolborane (HBpin) 的反应导致磷烯氧化物还原并形成O(Bpin)2。相比之下，磷烯氧化物OPn-Bu3与HB(C6F5)2或B(C6F5)3反应仅生成供体-受体加合物。化合物3与HNPt-Bu3反应生成磷铵烷硼酸盐[t-Bu3PNH2][(Bpin(OBpin)2]6，而与Cp2ZrMe2的反应则生成物种Cp2Zr(OBpin)2。

  DOI：

  10.1039/b504246a
• 作为产物：
  描述：

  三丁基膦 、 N-chlorohexamethyldisilazane 以 乙醚 为溶剂， 生成 N-Trimethylsilyl-tri-n-butyl-phosphinimin
  参考文献：
  名称：

  Pinchuk,A.M. et al., Journal of general chemistry of the USSR, 1972, vol. 42, p. 2111

  摘要：

  DOI：

文献信息

• Steric Effects in Metathesis and Reduction Reactions of Phosphinimines with Catechol- and Pinacolboranes
  作者：Sarah Hawkeswood、Pingrong Wei、James W. Gauld、Douglas W. Stephan

  DOI：10.1021/ic050230k

  日期：2005.6.1

  phosphinimine and borane affording reduction of the phosphinimine to phosphine with concurrent formation of borylamine is proposed. Computational studies were performed to probe the steric effects on these reactions of phosphinimine and borane. Model reactions involving t-Bu(3)PNH showed a lower activation barrier for protonolysis in comparison to phosphinimine reduction. In contrast, for the smaller phosphinimine

  已通过缔合间位合成了一系列通式为（mu-（R（3）PN）Bcat）（x）（）（cat = O（2）C（6）H（4））的儿茶酚基-次膦酰亚胺配合物反应。对于R = Et，n-Bu，Ph和i-Pr，R（3）= n-Bu t-Bu（2）X射线晶体学以及溶液NMR光谱和反应性研究表明，这些物质是二聚体。在R = t-Bu的情况下，空间拥堵导致单体种类t-Bu（3）PNBcat。同样，R（t-Bu）（2）PNH（R = n-Bu，t-Bu）和i-Pr（3）PNH与频哪醇硼烷（HBO（2）C（2）Me（4）= HBpin的反应）导致n-Bu（t-Bu（2））PNBpin，t-Bu（3）PNBpin和i-Pr（3）PNBpin的形成。较小的膦亚胺R（3）PNH（R = Et或n-Bu）与频哪醇硼烷（HBpin）的类似反应生成游离膦和含硼的产物HN（Bpin）（2）。在R（3）PNPh或R（3）PNAd（R
• Appel,R.; Schoeler,H., Chemische Berichte, 1977, vol. 110, p. 2382 - 2385
  作者：Appel,R.、Schoeler,H.

  DOI：——

  日期：——
• Preparation and properties of bis(phosphoranylidene)ammonium chlorides
  作者：Terence W. Rave

  DOI：10.1021/jo01286a038

  日期：1967.11
• Boron and Aluminum Complexes of Sterically Demanding Phosphinimines and Phosphinimides
  作者：Silke Courtenay、Denise Walsh、Sarah Hawkeswood、Pingrong Wei、Anjan Kumar Das、Douglas W. Stephan

  DOI：10.1021/ic0700351

  日期：2007.4.30

  Reactions of sterically demanding phosphinimines R3PNH [R = i-Pr (1), t-Bu (2)] were examined. Reactions with B(C6F5)(3) formed the adducts (R3PNH)B(C6F5)(3) [R = i-Pr (3), t-Bu (4)] in high yield. On the other hand, 2 reacts with HB(OBu)(2), evolving H-2 to give t-Bu3PNB(OBu)(2) (5). The reaction of 2 equiv of 2 with BH3 center dot SMe2 affords the species (t-Bu3PN)(2)BH (6). In contrast, the reaction of n-Bu(t-Bu)(2)PNH with BH3 center dot SMe2 results in the formation of the robust adduct n-Bu(t-Bu)(2)PNH center dot BH3 (8). An alternative route to borane-phosphinimide complexes involves Me3SiCl elimination, as exemplified by the reaction of BCl2Ph with n-Bu3PNSiMe3, which gives the product n-Bu3PNBCl(Ph) (9). The corresponding reactions of the parent phosphinimines 1 and 2 with AlH3 center dot NMe2Et give the dimers [(mu-i-Pr3PN)AlH2](2) (10) and [(mu-t-Bu3PN)AlH2](2) (11). Species 11 reacts further with Me3SiO3SCF3 to provide [(mu-t-Bu3PN)AlH(OSO2CF3)](2) (12). The reaction of the lithium salt [t-Bu3PNLi](4) (13) with BCl3 proceeds smoothly to give t-Bu3PNBCl2 (14), which is readily alkylated to give t-Bu3PNBMe2 (15). Subsequent reaction of 15 with B(C6F5)(3) results in methyl abstraction and the formation of [(mu-t-Bu3PN)BMe](2)[MeB(C6F5)(3)](2) (16). The reaction of 13 in a 2:1 ratio with BCl3 gives the salt [(t-Bu3PN)(2)B]Cl (17). This species can be methylated to give (t-Bu3PN)(2)BMe (18), which undergoes subsequent reaction with [Ph3C][X] (X = [B(C6F5)(4)], [PF6]) to form the related salts [(t-Bu3PN)(2)B][B(C6F5)(4)] (19) and [(t-Bu3PN)(2)B][PF6] (20), respectively. Analogous reactions with [Ph3C][BF4] afforded [t-Bu3PNBF2](2) (21). Compounds 3, 4, 6, 8, 11, 12, 17, 19, and 21 were characterized by X-ray crystallography.
• Bartsch, Rainer; Stelzer, Othmar, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1982, vol. 37, # 3, p. 267 - 271
  作者：Bartsch, Rainer、Stelzer, Othmar

  DOI：——

  日期：——