N,N,N'-tris(trimethylsilyl)dichloroaminoiminophosphorane | 58972-01-3

• 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,N,N'-tris(trimethylsilyl)dichloroaminoiminophosphorane
• 英文别名: tris-trimethylsilanyl-phosphoramidimidic acid dichloride；Trimethylsilylimino-bis(trimethyl-silyl)aminodichlorophosphorane；[[[[bis(trimethylsilyl)amino]-dichloro-λ5-phosphanylidene]amino]-dimethylsilyl]methane
• CAS: 58972-01-3
• 化学式: C₉H₂₇Cl₂N₂PSi₃
• 分子量: 349.463
• InChiKey: YKIGKRNZETZJNL-UHFFFAOYSA-N

物化性质

• 沸点：
  303.4±25.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.22
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N,N'-tris(trimethylsilyl)dichloroaminoiminophosphorane 、 五氯化钽 以 二氯甲烷 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  全卤代无环和金属环化钽（V）磷酰氨基络合物的合成和反应性：发现意外的配体偶联反应以形成新型磷腈鎓盐的发现。

  摘要：

  TaCl5与单当量的Cl3P = NSiMe3的反应导致分离出全卤化（磷酸氨基铵）钽（V）配合物TaCl4（N = PCl3）（1）。1与过量的THF反应并随后冷却产生TaCl4（N = PCl3）（THF）（1.THF）晶体，该晶体具有扭曲的八面体Ta中心，且THF分子反式配位于磷氨基胺配体。1与氨基磷氨基苯胺（Me3Si）2NPCl2 = NSiMe3的反应导致[3 +1]环缩合反应形成金属环配合物TaCl3（N = PCl3）[N（SiMe3）PCl2N（SiMe3）]（2） ，其中包含一个TaNPN四元环和一个磷酸氨基氨基配体（N = PCl3）。（Me3Si）2NPCl2 = NSiMe3与TaCl5之间类似的[3 +1]环缩合反应导致TaCl4 [N（SiMe3）PCl2N（SiMe3）]的分离（3）。尝试通过HCl质子分解从Ta中心在2中裂解NPN配体，这导致了异常的氨基磷酸

  DOI：

  10.1021/ic000988y

文献信息

• Synthesis and characterization of perhalogenated diazaphosphametalletidines containing transition metals from group 4 and 5
  作者：Eric Rivard、Andrew R. McWilliams、Alan J. Lough、Ian Manners

  DOI：10.1039/b109905c

  日期：——

  The preparation and characterization of the novel perhalogenated diazaphosphametalletidines, Cl3M[N(SiMe3)PCl2N(SiMe3)]·THF, M = Ti, Zr and Hf 2–4 and Cl4Nb[N(SiMe3)PCl2N(SiMe3)] 5 are reported. In addition, a new high yield preparation of the previously synthesized metallacycle Cl3Ti[N(SiMe3)PCl2N(SiMe3)] 1 is described. All reported complexes were synthesized by [3 + 1] cyclocondensation reactions involving the aminoiminophosphorane, (Me3Si)2NPCl2NSiMe3, and corresponding metal halides in dichloromethane. When 2.5 equivalents of (Me3Si)2NPCl2NSiMe3 were reacted with NbCl5 a complex series of products was identified by 31P1H} NMR spectroscopy; crystals of the unusual heterocycles [Cl3NbN(SiMe3)PCl2N}2Cl2NbN(SiMe3)PCl2N(SiMe3)}] 6 and [Cl2NbN(SiMe3)PCl2N(SiMe3)}]2-μ-Cl(NPCl2N) 7 were isolated. Complex 7 contains the first example of a ClNbNPNNb six-membered ring. Structural characterization by single-crystal X-ray diffraction is also reported for metallacycles 2, 3, and 5–7.

  报告了新型全卤化重氮膦甲脒 Cl3M[N(SiMe3)PCl2N(SiMe3)]-THF （M = Ti、Zr 和 Hf 2-4）和 Cl4Nb[N(SiMe3)PCl2N(SiMe3)] 5 的制备和表征。此外，还介绍了以前合成的金属环 Cl3Ti[N(SiMe3)PCl2N(SiMe3)] 1 的一种新的高产率制备方法。所有报告的配合物都是通过氨基亚氨基磷烷、(Me3Si)2NPCl2NSiMe3 和相应的金属卤化物在二氯甲烷中发生 [3 + 1] 环缩合反应合成的。当 2.5 个当量的 (Me3Si)2NPCl2NSiMe3 与 NbCl5 反应时，通过 31P1H} NMR 光谱鉴定出了一系列复杂的产物。通过 31P1H} NMR 光谱鉴定出了一系列复杂的产物；分离出了不同寻常的杂环 [Cl3NbN(SiMe3)PCl2N}2Cl2NbN(SiMe3)PCl2N(SiMe3)}] 6 和 [Cl2NbN(SiMe3)PCl2N(SiMe3)}]2-μ-Cl(NPCl2N) 7 的晶体。络合物 7 包含第一个 ClNbNPNNb 六元环。此外，还报告了通过单晶 X 射线衍射对金属环 2、3 和 5-7 进行的结构表征。
• Synthesis, Properties, and Bishomoaromaticity of the First Tetrahalogenated Derivative of a 1, 5-Diphosphadithiatetrazocine: A Combined Experimental and Computational Investigation
  作者：Tristram Chivers、Robert W. Hilts、Peng Jin、Zhongfang Chen、Xin Lu

  DOI：10.1021/ic902428j

  日期：2010.4.19

  The first example of a tetrahalogenated derivative of a diphosphadithiatetrazocine, 1,5-Cl2P(NSN)(2)PCl2 (3), was synthesized by cyclocondensation of a 2:1 mixture of SCl2 and SO2Cl2 with Cl2P(NSiMe3)N(SiMe3)(2) in CH2Cl2. The heterocycle 3 was isolated as an orange, moisture-sensitive, thermally labile solid and characterized by mass spectrometry, P-31 NMR, and UV visible spectroscopy, The low-field P-31 NMR chemical shift (93.7 ppm) is indicative of a cross-ring S-S interaction in the eight-membered P2N4S2 ring, and this conclusion is supported by densityfunctional computations. Compound 3 exhibits unusual physical properties compared with those of the known tetraalkyl or aryl derivatives; mild heating (90 degrees C) produces an orange rubbery material. The bishomoaromatic character of the diphosphadithiatetrazocine 1,5-R2P(NSN)(2)PR2 (R = Me, Cl, F) is evinced by the negative nucleusindependent chemical shift (NICS) values, and the through-space bishomoconjugation in the eight-membered ring decreases with increasing electronegativity of the substituents attached to the P atoms.