6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl(Cy) | 301525-54-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl(Cy)
• 英文别名: (1R,3S,5S,7R)-8-cyclohexyl-1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane
• CAS: 301525-54-2
• 化学式: C₁₆H₂₇O₃P
• 分子量: 298.362
• InChiKey: PHMGOXQGRDVSNQ-CAOSSQGBSA-N

物化性质

• 沸点：
  354.6±42.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl(Cy) 以 二氯甲烷 为溶剂， 以68%的产率得到trans-[PtCl₂(6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl(Cy))2]
  参考文献：
  名称：

  General Routes to Alkyl Phosphatrioxaadamantane Ligands

  摘要：

  The secondary phosphine CgPH (CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl group) is made in 50% yield by a modification of the literature method (avoiding high pressures of PH3) by bubbling PH3 through an acidified solution of 2,4-pentanedione at 0 degrees C. Under similar conditions the ethyl analogue (Et)CgPH is formed from 3,5-heptanedione in 75% yield. The halophosphines CgPCl and CgPBr are made by treatment of CgPH with N-halosuccinimide. CgPBr is also made by treatment of CgPH with Br-2. Three methods are described for the synthesis of CgPR, where R = alkyl: (a) the previously reported acid-catalyzed condensation reaction of RPH2 with 2,4-pentanedione, which has been extended to R = Pr-i; (b) treatment of CgP(BH3)Li with RX followed by borane deprotection with Et2NH, which has been used for R = Pr-i, benzyl, n-C20H41; (c) treatment of CgPBr with RMgX, which has been used for R = Pr-i, Me. The complexes [PtC12(CgPH)(2)] (1), [PdCl2(CgPH)(2)] (2), [PdCl2(CgPR)(2)] (where R = Pr-i (3a), Cy (3b)), and [PtCl2(CgPR)(2)] (where R = Pr-i (4a), Cy (4b), n-C20H41 (4c)) are described. The crystal structures of CgPH, CgPCl, [CgP(CH2Ph)(2)]Br, CgP(n-C20H41), and complexes 1, 3b, and 4c are reported. From the v(CO) values for trans-[RhCl(CO)(CgPX)(2)], the sigma-donor/pi-acceptor properties of CgPX are in the order X = Pr-i > Me > Ph > H > Cl.

  DOI：

  10.1021/om800141y

文献信息

• Titanium Complexes of Sterically Demanding Cage-Phosphinimide Ligands
  作者：Charles-Antoine Carraz、Douglas W. Stephan

  DOI：10.1021/om0003178

  日期：2000.9.1

  titanium complexes CpTiCl2(NPR(C6H4O3Me4)) (R = Ph (6), Cy (7)) and CpTiMe2(NPR(C6H4O3Me4)) (R = Ph (8), Cy (9)). Preliminary screening for catalytic activity in ethylene polymerization employing either methylalumoxane (MAO) or [Ph3C][B(C6F5)4] as the activator showed minimal catalytic activity. These observations were probed via reactions of these complexes with AlMe3, MAO, or [Ph3C][B(C6F5)4]. Reaction

  已经制备了已知的配体PPh（C 6 H 4 O 3 Me 4）（1）及其类似物PCy（C 6 H 4 O 3 Me 4）（2）。在后者的合成中，二膦类（PCy）2（C 6 H 2 O 3 Me 4）（3）也作为次要产物被分离出来。笼型膦1和2与Me 3 SiN 3的反应氧化为相应的（三甲基甲硅烷基）膦亚胺Me3 SiNPR（C 6 H 4 O 3 Me 4）（R = Ph（4），Cy（5））。随后的反应得到钛络合物CpTiCl 2（NPR（C 6 H 4 O 3 Me 4））（R = Ph（6），Cy（7））和CpTiMe 2（NPR（C 6 H 4 O 3 Me 4）） （R ＝ Ph（8），Cy（9））。使用甲基铝氧烷（MAO）或[Ph]初步筛选乙烯聚合中的催化活性作为活化剂的3 C] [B（C 6 F 5）4 ]显示出最小的催化活性。通过这些配合物与AlMe 3，MAO或[Ph 3 C]