cis-[(2,6-iPr2C6H3NH)(t-BuNP)]2 | 750586-96-0

• 英文名称: cis-[(2,6-iPr2C6H3NH)(t-BuNP)]2
• 英文别名: cis-[(2,6-iPr2C6H3NH)(tBuNP)]2
• CAS: 750586-96-0
• 化学式: C₃₂H₅₄N₄P₂
• 分子量: 556.755
• InChiKey: QMLIYVYQIOKDGL-MAZIBIHTSA-N

物化性质

• 沸点：
  554.8±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.37
• 重原子数：
  38.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  30.54
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  cis-[(2,6-iPr2C6H3NH)(t-BuNP)]2 在 n-BuLi 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 生成 [(((2,6-diisopropylphenyl)NP(Me)N(t-Bu)AlMe2)Cr(((2,6-diisopropylphenyl)NP(Me)(AlMe3)N(t-Bu))AlMe(μ-Me))]
  参考文献：
  名称：

  Preparation and Characterization of a Switchable Single-Component Chromium Trimerization Catalyst

  摘要：

  Reaction of [(Ar)NPN(t-Bu)](2)Cr (2) with Me3Al afforded {[(Ar)NP(Me)N(t-Bu)]AlMe2}Cr{[(Ar)NP(Me)-(AlMe3)N(t-Bu)]AlMe(mu-Me)} (3), in which the ligand's P atom has been alkylated and one AlR2 residue retained by the chelating framework. One of the two ligands also retained an additional Me3Al unit via coordination to the alkylated P atom. Complex 3 provides the first case of a selective ethylene trimerization catalyst with high activity and excellent selectivity, producing 1-hexene upon exposure to ethylene at 80 degrees C. Furthermore, upon treatment with MAO, complex 3 acts as a nonselective catalyst, producing a statistical mixture of oligomers with the highest ever observed activity. In addition, upon treatment with [(i-Bu)(2)Al](2)O, the complex acts as a highly active polymerization catalyst.

  DOI：

  10.1021/om800563w

文献信息

• [Bis(amido)cyclodiphosph( <scp>III</scp> )azane]dichlorozirconium Complexes for Ethene Polymerization
  作者：Kirill V. Axenov、Martti Klinga、Markku Leskelä、Vasily Kotov、Timo Repo

  DOI：10.1002/ejic.200400296

  日期：2004.12

  coordination between the metal and a nitrogen atom from the cyclodiphosph(III)azane ring. After methylaluminoxane activation, these complexes exhibit moderate to high activities in ethene polymerization and produce high molar mass polyethene (Mw up to 1100 kg/mol). Polymerization experiments reveal that the behavior of bis(amido)cyclodiphosph(III)azane-based ZrIV catalysts depends on the nature and steric bulkiness

  一系列带有庞大顺式双（氨基）环二磷（III）氮烷配体的新型二氯化锆配合物，[(RN)2(tBuNP)2]ZrCl2 [R = 苯基 (7), 二苯基甲基 (8), 2,6-二乙基苯基 (9)、2,5-二-叔丁基苯基 (10) 和 2,6-二异丙基苯基 (11)] 通过两步合成路线以高产率制备。通过 X 射线分析确定的 cis-[(Ph2CHN)(tBuNP)]2Zr(NMe2)2 (8a) 的结构表明，锆原子具有扭曲的三角双锥构型，由四个等距的金属-酰胺氮键组成以及金属与环二磷 (III) 氮烷环中的氮原子之间的额外配位。甲基铝氧烷活化后，这些配合物在乙烯聚合中表现出中到高的活性，并产生高摩尔质量的聚乙烯（Mw 高达 1100 kg/mol）。聚合实验表明，双（酰氨基）环二磷（III）氮烷基 ZrIV 催化剂的行为取决于酰氨基取代基的性质和空间体积、反应温度、MAO/锆比以及单体压力。(©
• New Bulky Bis(amino)cyclodiphosph( <scp>III</scp> )azanes and Their Titanium( <scp>IV</scp> ) Complexes: Synthesis, Structures and Ethene Polymerization Studies
  作者：Kirill V. Axenov、Vasily V. Kotov、Martti Klinga、Markku Leskelä、Timo Repo

  DOI：10.1002/ejic.200300487

  日期：2004.2

  cis-[(2,4-Me2C6H3N)(PN-tBu)]2Li2(THF)2. The crystal structure of cis-[(2,4-Me2C6H3N)(PN-tBu)]2Li2(THF)2 (9) consists of a heterocube of two lithium atoms, two nitrogen atoms and a cyclodiphosph(III)azane ring. Transmetallation of Li compounds by TiCl4 was unselective and led to a complex mixture of products. The direct reaction of cis-bis(amino)cyclodiphosph(III)azanes with Ti(NMe2)4 is the most efficient

  双(氨基)环二磷(III)氮杂顺式-[(RNH)(PN-tBu)]2, R = 2,6-iPr2C6H3 (2), 2-tBuC6H4 (3), 2-CF3C6H4 (4), 2, 5-tBu2C6H3 (5), Ph2CH (6), 2,4-Me2C6H3 (7), 2,6-Et2C6H3 (8), 在 Et3N 存在下通过顺式-(ClPN-tBu )2 (1) 与相应的庞大芳基和烷基胺。双（氨基）环二磷（III）氮杂烷 2-8 采用热力学稳定的顺式构型——这是有效形成金属络合物的先决条件。用 nBuLi 对双（氨基）环二磷 (III) 氮烷进行去质子化，慢慢得到相应的盐，cis-[(2,4-Me2C6H3N)(PN-tBu)]2Li2(THF)2。cis-[(2,4-Me2C6H3N)(PN-tBu)]2Li2(THF)2 (9) 的晶体结构由两个锂原子、两个氮原子和一个环二磷 (III)
• Bis(amido)cyclodiphosph(III)azane Hafnium Complexes and Their Activation by Tris(perfluorophenyl)borane
  作者：Kirill V. Axenov、Martti Klinga、Markku Leskelä、Timo Repo

  DOI：10.1021/om0492303

  日期：2005.3.1

  Bis(amido) hafnium complexes [(RN)(t-BuNP)]2HfCl2 (R = 2,6-i-Pr2C6H3 (5), 2,5-t-Bu2C6H3 (6)) bearing a N-tert-butyl cyclodiphosph(III)azane bridge were prepared by direct metalation of corresponding ligand precursors with Hf(NMe2)4 followed by chlorination by Me3SiCl. Complexes 5 and 6 and the already known [(t-BuN)(t-BuNP)]2HfCl2 (4) were subsequently converted to their methyl derivatives [(RN)(t-BuNP)]2HfMe2

  双（酰胺基）ha络合物[（RN）（t- BuNP）] 2 HfCl 2（R = 2,6- i- Pr 2 C 6 H 3（5），2,5- t- Bu 2 C 6 H 3（6））轴承ñ -叔丁基cyclodiphosph（III）azane桥通过相应配体前体与HF（NME的直接金属化制备2）4，随后通过氯化我3的SiCl。配合物5和6以及已知的[（t-BUN）（叔BuNP）] 2的HfCl 2（4）随后转化成其甲基衍生物[（RN）（叔BuNP）] 2 HfMe 2通过在Et烷基化通过将MeMgBr 2 O.的固态结构[ （t- BuN）（t- BuNP）] 2 HfMe 2（7）在金属中心揭示了高度变形的三角-金字塔形构型。用B（C 6 F 5）3活化二甲基配合物导致相应阳离子种类的产生，对此进行了研究11 H，13 C，31 P和19 F NMR。在固态状态下，[（（t- BuN）（t-