(N(Me3SiNCH2CH2)3)ZrPHPh | 937801-06-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (N(Me3SiNCH2CH2)3)ZrPHPh
• 英文别名: [(N(CH2CH2NSiMe3)3)Zr(phenylphosphido)]；(N(CH2CH2NSiMe3)3)Zr(PHPh)；(N(CH2CH2NSiMe3)3)ZrPHPh；(N3N)ZrPHPh
• CAS: 937801-06-4
• 化学式: C₂₁H₄₅N₄PSi₃Zr
• 分子量: 560.069
• InChiKey: HDSNQMPXYXBURS-UHFFFAOYSA-N

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：

  (N(Me3SiNCH2CH2)3)ZrPHPh 以 苯 为溶剂， 反应 14.0h， 生成
  参考文献：
  名称：

  A general synthesis of phosphaalkenes at zirconium with liberation of phosphaformamides

  摘要：

  报道了一种通用的、原子经济性合成膦杂烯的方法，通过锆促进下的伯烷基或芳基膦与芳基或烷基异氰化物的直接偶联反应完成。磷元素所形成的配体可以通过与有机亲电试剂反应从锆上释放出来，形成磷杂甲酰胺化合物。

  DOI：

  10.1039/c2dt32322b
• 作为产物：
  描述：

  (N₃N)ZrCl 以 乙醚 、 氘代苯 为溶剂， 生成 (N(Me3SiNCH2CH2)3)ZrPHPh
  参考文献：
  名称：

  Selective Dehydrocoupling of Phosphines by Triamidoamine Zirconium Catalysts

  摘要：

  New zirconium triamidoamine complexes (N3N)ZrR (N3N = N(CH2CH2NSiMe3)(3)(3-); R = Me, < BO > 1 ; PHPh, < BO > 2 ; PHCy, < BO > 4) are effective catalysts for the dehydrocoupling of primary and secondary phosphines and select for the diphosphine product. Mechanistic analysis revealed that metal-catalyzed P-P bond formation occurs via sigma-bond metathesis steps.

  DOI：

  10.1021/om070189o
• 作为试剂：
  描述：

  diphenylgermane 、 苯基膦 在 (N(Me3SiNCH2CH2)3)ZrPHPh 作用下， 以 苯 为溶剂， 以77%的产率得到Ph2GeHPHPh
  参考文献：
  名称：

  伯膦与硅烷和锗烷的锆催化杂脱氢偶联。

  摘要：

  三酰氨基胺负载的锆络合物催化伯膦与硅烷和锗烷的杂脱氢偶联。在这种催化中，仅观察到P-Si或P-Ge产物，没有竞争性的PP键形成。观察到磷酸盐配合物（N 3 N）ZrPHR（N 3 N ＝ N（CH 2 CH 2 NS 1 Me 3）33-，R ＝ Ph，2； Cy，3）为催化剂静止状态，并且对配合物2进行了结构表征。

  DOI：

  10.1021/ic7013144

文献信息

• Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes
  作者：Andrew J. Roering、Sarah E. Leshinski、Stephanie M. Chan、Tamila Shalumova、Samantha N. MacMillan、Joseph M. Tanski、Rory Waterman

  DOI：10.1021/om100216f

  日期：2010.6.14

  (N3N = N(CH2CH2NSiMe3)33−; R = alkyl, aryl; R′ = R, H), have been shown to catalyze the hydrophosphination of terminal alkynes as well as that of symmetric aryl and alkyl carbodiimides. A mechanism based on insertion of the substrate into the Zr−P bond is proposed on the basis of competition experiments and model examples of stoichiometric insertion reactions of polar, small-molecule substrates possessing

  Triamidoamine支持锆膦配合物，（N 3 N）ZrPRR'（N 3 N = N（CH 2 CH 2 NSiMe 3）3 3- ; R =烷基，芳基; R'= R，H），已经显示出催化末端炔烃以及对称的芳基和烷基碳二亚胺的氢磷化。在竞争实验和具有C proposedO，C═N，C≡N和C的极性小分子底物的化学计量插入反应的模型实例的基础上，提出了基于将底物插入Zr-P键的机理。 C═S功能进入Zr-P键。插入产物（N 3 N）ZrN═C（PHCy）Ph（4），（N 3的分子结构N）ZrN═C（PPH 2）PH（5），和（N 3 N）ZrPhNC（O）PPH 2（11），以及（N 3 N）的Zr [η 2（N，N-） - （我PrN）2 C（PPh 2）]（9）是碳二亚胺催化加氢磷酸化的关键中间体，现已确定。
• Insertion of benzyl isocyanide into a Zr–P bond and rearrangement. Atom-economical synthesis of a phosphaalkene
  作者：Samantha N. MacMillan、Joseph M. Tanski、Rory Waterman

  DOI：10.1039/b709506f

  日期：——

  Reaction of (N(3)N)ZrPHPh (N(3)N=N(CH(2)CH(2)NSiMe(3))(3)(3-)) with PhCH(2)N[triple bond]C affords the 1,1-insertion product (N(3)N)Zr[C(PHPh)=NCH(2)Ph], which thermally rearranges to the phosphaalkene-containing complex, (N(3)N)Zr[N(CH(2)Ph)C(H)=PPh].

  （N（3）N）ZrPHPh（N（3）N = N（CH（2）CH（2）NSiMe（3））（3）（3-））与PhCH（2）N [三键]的反应C提供1,1插入产物（N（3）N）Zr [C（PHPh）= NCH（2）Ph]，该产物热重排为含磷烯烃的配合物（N（3）N）Zr [N （CH（2）Ph）C（H）＝ PPh]。
• General Preparation of (N₃N)ZrX (N₃N = N(CH₂CH₂NSiMe₃)₃³⁻) Complexes from a Hydride Surrogate
  作者：Andrew J. Roering、Annalese F. Maddox、L. Taylor Elrod、Stephanie M. Chan、Michael B. Ghebreab、Kyle L. Donovan、Jillian J. Davidson、Russell P. Hughes、Tamila Shalumova、Samantha N. MacMillan、Joseph M. Tanski、Rory Waterman

  DOI：10.1021/om8008684

  日期：2009.1.26

  A homoleptic triamidoamine zirconium complex featuring a metalated trimethylsilyl substituent, [k(5)- (Me3SiNCH2CH2)(2)NCH2CH2NSiMe2CH2]Zr (1), was synthesized by reaction of Zr(CH2Ph)(4) with N(CH(2)CH(2)NHSiN(4)e(3))(3) followed by sublimation. Complex 1 is a general precursor to a family of complexes with the formulation (N3N)ZrX (N3N = N(CH2CH2NSiMe3)(3)(3-), X = anionic ligand) by reactions that parallel expected reactivity of a hydride derivative. Treatment of 1 with phosphines, amines, thiols, alkynes, and phenol resulted in the formation of new, pseudo-C-3v-symmetric (N3N)ZrX complexes (X = phosphido, amido, alkynyl, thiolate, or phenoxide) via element-H bond activation. Thus, the reactivity of complex I is that best described as a hydride surrogate. For example, complex I reacted with PhPH2 at ambient temperature to provide (N3N)ZrPHPh (2) in 86% yield. Density functional theory studies and X-ray crystal structures provide a general overview of the bonding in these complexes, which appears to be highly ionic. In general, there is little evidence for ligand-to-metal pi-bonding for the pseudoaxial X ligand in these complexes except for strongly pi-basic terminal amido ligands. The limited pi-bonding appears to be the result of competitive pi-donation by the pseudoequatorial amido arms of the triamidoamine ancillary ligand. Thus, the relative Zr-X bond energies are governed by the basicity of the anionic ligand X. Solid-state structures of phosphido (3, 4, 5), amido (10), and thiolate (15) complexes support the computational results.