| 780773-71-9

• CAS: 780773-71-9
• 化学式: C₂₆H₄₀Cl₃NP₂Zr
• 分子量: 626.141
• InChiKey: PODQIPUSSXGINX-UHFFFAOYSA-K

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：

  二甲基镁 、 在 1,4-二氧六环 作用下， 以 乙醚 为溶剂， 以31%的产率得到[(PNP)Zr(CH₃)₃]
  参考文献：
  名称：

  螯合物增强的膦配位可实现α-抽象化，生成锆炔烃

  摘要：

  刚性PNP钳位配体（PNP =双（邻-二异丙基膦酰基芳基）胺的去质子化阴离子）显示可稳定（Zr CHR）2+片段。（PNP）Li（THF）（2-THF）含有P-Li键，这是通过在溶液31 P NMR光谱中观察到Li-P偶联以及通过在固态下进行X射线结构测定所证实的。2-THF与ZrCl 4（Et 2 O）2反应，得到（PNP）ZrCl 3（3）。（PNP）ZrCl 3（3）可以用RCH 2 MgCl烷基化，得到（PNP）Zr（CH 2 R）3（4a - c）。（PNP）ZrMe 3（4a）是热稳定的，并且其固态结构的特征在于八面体几何形状的严重变形。（PNP）Zr（CH 2 R）3（R =苯基（4b）或对甲苯基（4c））化合物在环境温度下经历α吸收，得到可分离的Zr烷基/亚烷基（PNP）Zr（CHR）（CH 2 R）（5b，c）。该反应遵循一阶速率定律（在298 K≈2.3 h时为t 1/2）。活化参数由VT

  DOI：

  10.1021/om049670u
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 Li[N(2-P(CHMe2)2-4-MeC6H3)2] 以 甲苯 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  亚甲基锆配合物的反应性研究：基团转移和亚甲基化反应

  摘要：

  The zirconium methylidene complex (PNP)-Zr=CH2(OAr) (1; PNP = N[2-(PPr2)-Pr-i-4-methylphenyl](2)(-), Ar = 2,6-(Pr2C6H3)-Pr-i), prepared from photolysis of (PNP)Zr-(CH3)(2)(OAr), can engage in incomplete and complete methylidene group transfer reactions with CO, CDCl3, cyclododecanone, and benzophenone. When CO was treated with 1, methylenation occurred via the putative metalloketene adduct [(PNP)Zr(OCCH2)(OAr], which ultimately afforded the C-C coupled enolate dimer [(PNP)Zr-(OAr)](2)(OCH2C=CCH2O) (2). Addition of CDCl3 to 1 rapidly resulted in formation of (PNP)ZrCl2(OAr) (3) along with liberation of d(1)-vinyl chloride, H2C=CDCl. Complex 3 could be readily prepared independently from (PNP)ZrCl3 and 1 equiv of NaOAr. Wittig reactivity was observed between 1 and cyclododecanone to afford methylenecyclododecane. Similarly, treating 1 with the ketone OCPh2 resulted in methylenation of the ortho position followed by tautomerization to produce the chelated alkyloxide complex (PNP)Zr(OAO[OCHPh(C6H4)-CH2] (4). In addition to the isolation of 4, complex 1 also engages in a cross-metathesis reaction involving the methylidene and ketone oxygen of benzophenone, as well as in olefin metathesis involving the formed olefin H2C=CPh2. Complexes 2-4 have been fully characterized, including solid-state structural analysis, and proposed mechanisms for the formation of species such as 2-4 are presented and discussed.

  DOI：

  10.1021/acs.organomet.6b00594