bis(tri-tert-butylphosphinimide)TiMe2 | 226903-18-0

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: bis(tri-tert-butylphosphinimide)TiMe2
• 英文别名: ((t-Bu)3PN)2TiMe2；(t-Bu3PN)2TiMe2
• CAS: 226903-18-0
• 化学式: C₂₆H₆₀N₂P₂Ti
• 分子量: 510.603
• InChiKey: SPXJQFNXUONRSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.26
• 重原子数：
  31.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.72
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  bis(tri-tert-butylphosphinimide)TiMe2 、 叔丁基硫醇 以 苯 为溶剂， 以89%的产率得到(t-Bu₃PN)2Ti(Me)(St-Bu)
  参考文献：
  名称：

  磷酰亚胺亚硫酰钛配合物的合成，结构和反应性

  摘要：

  使用硫醇盐进行氯化物易位或硫醇对金属碳键的质子分解，制备了一系列的钛-次亚膦酰亚胺硫醇盐配合物。以这些方式，得到下列物种：CPTI（NPR ' 3）（SR）2（R'=异PR，R = CH 2博士3 ;博士4，叔卜5，（SR）2 = S 2（ CH 2）2 6，S 2（CH 2）3 7，S 2（CH 2）2 C 6 H4 8 ; R′＝t- Bu，R ＝ CH 2 Ph 9；m ＝1。Ph 10，t- Bu 11）；Cp（t- Bu 3 PN）TiMe（SPh）12；和（t- Bu 3 PN）2 Ti（SR）2（R ＝ CH 2 Ph 14； Ph 15，t- Bu 16）。（t -Bu 3 PN）2 TiMe 2与1当量的HSCH 2 Ph的反应产生了环金属化的物种17，（吨-Bu 3 PN）2的Ti（η 2 -SCHPh）。1当量的苯硫醇的类似反应生成了（t- Bu 3 PN）2 Ti（

  DOI：

  10.1021/om011042e
• 作为产物：
  描述：

  (Tritert-butyl-lambda5-phosphanylidene)azanide;trichlorotitanium(1+) 、 甲基溴化镁 以 乙醚 为溶剂， 以82%的产率得到bis(tri-tert-butylphosphinimide)TiMe2
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of the Phosphinimide Complexes (t-Bu₃PN)_nMX_4-n (M = Ti, Zr)

  摘要：

  The phosphinimide complexes (t-Bu3PN)TiCl3 (1) and (t-Bu3PN)(2)TiCl2 (4) are readily prepared in high yields from the stoichiometric reaction of t-Bu3PNSiMe3 and TiCl4, while (t-Bu3PN)(3)TiCl (11) is readily obtained from the reaction of t-Bu3PNLi and TiCl4. The analogous 1:1 or 2:1 reactions of ZrCl4 and t-Bu3PNLi afford mixtures of products, although in the 3:1 stoichiometric ratio (t-Bu3PN)(3)ZrCl (12) is isolable. These complexes are readily alkylated with a variety of reagents to give (t-Bu3PN)TiMe3 (2), (t-Bu3PN)Ti(CH2Ph)(3) (3), (t-Bu3PN)(2)TiMe2 (5), (t Bu3PN)(2)Ti(eta(3)-C3H5)(2) (6), (t-Bu3PN)(2)Ti(CH2Ph)(2) (7), (t-Bu3PN)(2)TiPh2 (8), (t-Bu3PN)(2)Ti(eta(5)-Cp)Cl (9), (t-B3PN)(2)Ti(eta(5)-CP)Me (10), (t-Bu3PN)(3)TiMe (13), (t-Bu3PN)(3)TiPh (14), (t-Bu3PN)(3)ZrMe (15), (t-Bu3PN)(3)Zr(CH2Ph) (16), and (t-Bu3PN)(3)Zr(eta(5)-Cp) (17). Subsequent reactions of some of these alkyl derivatives with [PhNMe2H][B(C6F5)(4)], [Ph3C]-[B(C6F5)(4)], Or B(C6F5)3 are investigated. A number of zwitterionic and cationic species complexes have been characterized. These include [(t-Bu3PN)Ti(CH2Ph)(2)( PhCH2)B(C6F5)(3)] (18), [(t- Bu3PN)(2)TiMe(PMe3)] [B(C6F5)(4)] (19), (t-Bu3PN)(2)TiMe (mu-MeB(C6F5)(3)) (20), (t-Bu-3-PN)(2)Ti(mu-MeB(C6F5)(3))(2) (21), and (t-Bu3PN)(2)Ti(C6F5)(2) (22). The implications of this chemistry are considered. Structural data for 1, 4, 5, 12, 18, 21, and 22 are described.

  DOI：

  10.1021/om0002069

文献信息

• Remarkably Active Non-Metallocene Ethylene Polymerization Catalysts
  作者：Douglas W. Stephan、Frédéric Guérin、Rupert E. v. H. Spence、Linda Koch、Xiaoliang Gao、Steve J. Brown、John W. Swabey、Qinyan Wang、Wei Xu、Peter Zoricak、Daryll G. Harrison

  DOI：10.1021/om981026q

  日期：1999.5.1

  complexes (t-Bu3PN)2TiCl2 (1) and (t-Bu3PN)2TiMe2 (2) were prepared and characterized crystallographically. Stoichiometric reactions of 2 with PhNMe2H[B(C6F5)4] in the presence of PMe3 afforded [(t-Bu3PN)2TiMe(PMe3)][B(C6F5)4] (3), while reaction of 2 with B(C6F5)3 affords (t-Bu3PN)2TiMe(μ-Me)B(C6F5)3 (4). Under laboratory conditions these compounds are effective ethylene polymerization catalysts. Under

  双（三-叔-butylphosphinimide）络合物（吨-Bu 3 PN）2的TiCl 2（1）和（吨-Bu 3 PN）2时间2（2）中制备和表征结晶。在PMe 3存在下2与PhNMe 2 H [B（C 6 F 5）4 ]的化学计量反应得到[（t- Bu 3 PN）2 TiMe（PMe 3）] [B（C 6 F 5））4 ]（3），同时2与B（C 6 F 5）3反应得到（t- Bu 3 PN）2 TiMe（μ-Me）B（C 6 F 5）3（4）。在实验室条件下，这些化合物是有效的乙烯聚合催化剂。在与商业相关的溶液聚合条件下，这些催化剂具有出色的活性。配合物2，当被Ph 3 C [B（C 6 F 5）4激活时制备具有窄多分散性的高分子量聚乙烯，其速率比约束几何催化剂（（C 5 Me 4 SiMe 2 N- t -Bu）TiX 2）快约4倍。这样，这些催化剂代表在商业上相关的聚合条件下与茂
• Divergent Pathways of C−H Bond Activation:  Reactions of (<i>t</i>-Bu₃PN)₂TiMe₂ with Trimethylaluminum
  作者：James E. Kickham、Frédéric Guérin、Douglas W. Stephan

  DOI：10.1021/ja0260972

  日期：2002.9.1

  The reaction of AlMe3 with (t-Bu3PN)(2)TiMe2 1 proceeds via competitive reactions of metathesis and C-H activation leading ultimately to two Ti complexes: [(mu(2)-t-Bu3PN)Ti(mu-Me)(mu(4)-C)(AlMe2)(2)](2) 2, [(t-Bu3PN)Ti(mu(2)-t-Bu3PN)(mu(3)-CH2)(2)(AlMe2)(2)(AlMe3)] 3, and the byproduct (Me2Al)(2)(u-CH3)(u-NP(t-Bu-3)) 4. X-ray structural data for 2 and 3 are reported. Compound 3 undergoes thermolysis to generate a new species [Ti(mu(2)-t-Bu3PN)(2)(mu(3)-CH2)(mu(3)-CH)(AlMe2)(3)] 5. Monitoring of the reaction of 1 with AlMe3 by P-31H-1} NMR spectroscopy revealed intermediates including (t-Bu3PN)TiMe3 6. Compound 6 was shown to react with AlMe3 to give 2 exclusively Kinetic studies revealed that the sequence of reactions from 6 to 2 involves an initial C-H activation that is a second-order reaction, dependent on the concentration of Ti and Al. The second-order rate constant k(1) was 3.9(5) x 10(-4) M-1 s(-1) (DeltaH(not equal) = 63(2) kJ/mol, DeltaS(not equal) = -80(6) J/mol.K). The rate constants for the subsequent C-H activations leading to 2 were determined to be k(2) = 1.4(2) x 10(-3) s(-1) and k(3) = 7(1) x 10(-3) s(-1). Returning to the more complex reaction of 1, the rate constant for the ligand metathesis affording 4 and 6 was k(met) = 6.1(5) x 10(-5) s-1 (DeltaH(not equal) = 37(3) kJ/mol, DeltaS(not equal) = -203(9) J/mol.K). The concurrent reaction of 1 leading to 3 was found to proceed with a rate constant of k(obs) of 6(1) x 10(-5) s(-1) (DeltaH(not equal) = 62(5) kJ/mol, DeltaS(not equal)= -118(17) J/mol.K). Using these kinetic data for these reactions, a stochastic kinetic model was used to compute the concentration profiles of the products and several intermediates with time for reactions using between 10 and 27 equivalents of AlMe3. These models support the view that equilibrium between 1.AlMe3 and 1.(AlMe3)(2) accounts for varying product ratios with the concentration of AlMe3. In a similar vein, similar equilibria account for the transient concentrations of 6 and an intermediate en route to 3. The implications of these reactions and kinetic and thermodynamic data for both C-H bond activation and deactivation pathways for Ti-phosphinimide olefin polymerization catalysts are considered and discussed.