[CH(3,5-Me2Pz)2-κ3-[N,C,N]]W(carbonyl)3(tri(p-tolyl)stannyl) | 586956-39-0

• 英文名称: [CH(3,5-Me2Pz)2-κ3-[N,C,N]]W(carbonyl)3(tri(p-tolyl)stannyl)
• 英文别名: [(CH(3,5-dimethylpyrazol-1-yl)2)W(CO)3Sn(p-CH3C6H5)3]；CH(3,5-Me2Pz)2W(CO)3Sn(p-MePh)3
• CAS: 586956-39-0
• 化学式: C₃₅H₃₆N₄O₃SnW
• 分子量: 863.256
• InChiKey: YRJBVUVEGORHEE-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：

  [CH(3,5-Me2Pz)2-κ3-[N,C,N]]W(carbonyl)3(tri(p-tolyl)stannyl) 、 四氯化锡 以 二氯甲烷 为溶剂， 以48%的产率得到[(CH(3,5-dimethylpyrazol-1-yl)2)W(CO)3Cl]
  参考文献：
  名称：

  Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

  摘要：

  Reaction of (isopropyl)diphenylstannylbis(3,5-dimethylpyrazol-1-yl)methane [(i-Pr)Ph2SnCH(3,5-Me(2)Pz)(2)] and tricyclohexylstannylbis(3,5-dimethylpyrazol-1-yl)methane [Cy3SnCH(3,5-Me(2)Pz)(2)] with W(CO)(5)THF in refluxing THF yields heterobimetallic complexes (i-Pr)Ph2SnCH(3,5-Me(2)Pz)(2)W(CO)(4) and Cy3SnCH(3,5-Me(2)Pz)(2)W(CO)(4), respectively. Treatment of these heterobimetallic complexes, R3SnCH(3,5-Me(2)Pz)(2)W(CO)(4) (R-3 = (i-Pr)Ph-2, Cy-3, Et-3), with I-2 results in the formation of a novel eta(t)-bis(pyrazol-1-yl)acyl complex CHC(O)(3,5-Me(2)Pz)(2)W(CO)(3)I, with the loss of the organotin group from the methine carbon. In addition, the reaction of R3SnCH(3,5-Me(2)Pz)(2)W(CO)(4) with SnCl4 in a 1:1 molar ratio gives heterotrimetallic complexes R3SnCH(3,5-Me(2)Pz)(2)W(Cl)(CO)(3)SnCl3 (R = Cy, Et). It is unexpected that these heterotrimetallic complexes are also reactive in solution. They change to a novel four-membered heterometallacyclic complex CH(3,5-Me(2)Pz)(2)W(CO)(3)Cl in dichloromethane solution at room temperature. Furthermore, this complex can also be obtained by the selective cleavage of the W-Sn bond in complexes CH(3,5-Me(2)Pz)(2)W(CO)(3)SnAr3 with SnCl4.

  DOI：

  10.1021/om800603p
• 作为产物：
  描述：

  tri(p-tolyl)stannyl-CH(3,5-Me2Pz)2W(carbonyl)4 生成 [CH(3,5-Me2Pz)2-κ3-[N,C,N]]W(carbonyl)3(tri(p-tolyl)stannyl)
  参考文献：
  名称：

  甲碳上有机锡基团修饰的双（吡唑-1-基）甲烷与W（CO）5 THF的反应生成新型异双核有机金属配合物

  摘要：

  通过使双（吡唑-1-基）甲基锂与有机锡卤化物反应，合成了在次甲基碳上具有有机锡基团的一系列新的双（吡唑-1-基）甲烷。已经详细研究了它们与W（CO）5 THF的反应，表明这些新的配体在用W（CO）5 THF处理后显示出多种反应活性，这取决于锡原子上取代基的性质。用W（CO）5 THF处理三芳基锡烷基双（吡唑-1-基）甲烷Ar 3 SnCHPz 2（Ar =苯基或对甲苯基; Pz =取代的吡唑）导致氧化锡碳（sp 3）结合到钨（0）中心以产生新型金属-金属键合配合物CHPz 2（CO）3 W-SnAr 3，其中发现了四元金属环，而双（吡唑-1-基）甲基化物起三齿态的作用单阴离子κ 3 - [N，C，N]螯合配体。当在吡唑环的4-位上存在烷基取代基时，可以分离出一些脱羰基中间体Ar 3 SnCHPz 2 W（CO）4。顺序地加热这些中间体也可以导致氧化加成的锡-碳（SP的3）键合到钨（0）中心，这意味着锡-碳的氧化加成反应（SP

  DOI：

  10.1021/om030221o

文献信息

• Reactivity of the Four-Membered Heterometallacycles CH(3,5-Me₂Pz)₂(CO)₃WSnAr₃ (Pz = Pyrazol-1-yl) with P(OR)₃:  Unexpected P−O/C Exchange Reactions in Phosphite
  作者：Xiao-Yan Zhang、Juan Hong、Hai-Bin Song、Liang-Fu Tang

  DOI：10.1021/om7003332

  日期：2007.7.30

  Reactions of CH(3,5-Me2Pz)2(CO)3WSnAr3 (Pz = pyrazol-1-yl; Ar = phenyl, p-tolyl) with P(OR)3 (R = methyl, isopropyl) under solvent-free conditions give the decarbonylated complexes CH(3,5-Me2Pz)2(CO)2(P(OR)3)WSnAr3. However, treatment of CH(3,5-Me2Pz)2(CO)3WSnAr3 with P(OMe)3 at elevated temperature results in unexpected P−O/C exchange reactions with the cleavage of the W−C bond to give the novel reductive

  CH（3,5-Me 2 PZ）2（CO）3 WSnAr 3（PZ =吡唑-1-基; Ar =苯基，对甲苯基）与P（OR）3（R =甲基，异丙基）的反应在无溶剂的条件下得到脱羰基的配合物CH（3,5-Me 2 PZ）2（CO）2（P（OR）3）WSnAr 3。然而，治疗CH（3,5--ME的2 PZ）2（CO）3 WSnAr 3与P（OME）3在高温下会导致意外的P-O / C交换反应，并裂解W-C键，得到新颖的还原消除产物（MeO）2 PCH（3,5-Me 2 PZ）2 W（CO）3。此外，即使在低温下，CH（3,5-Me 2 PZ）2（CO）3 WSnAr 3与P（OAr）3的反应也只能产生相似的还原消除产物（ArO）2 PCH（3,5- Me 2 PZ）2 W（CO）3。在这些新的钨（0）配合物，新形成的二芳基或二烷基二（3,5-二甲基吡唑-1-基）基亚充当中性三齿κ 3 [N，N，P]螯合配体。
• Unexpected Reactivity of CH(3,5-Me₂Pz)₂(CO)₃WSnAr₃ (Pz = pyrazol-1-yl; Ar = phenyl or <i>p</i>-tolyl) toward Hydrogen Halide
  作者：Liang-Fu Tang、Juan Hong、Zhen-Kang Wen

  DOI：10.1021/om0503895

  日期：2005.8.1

  Reaction of CH(3,5-Me(2)PZ)(2)(CO)(3)WSnAr3 (Pz = pyrazol-1-yl; Ar = phenyl or p-tolyl) with hydrogen halide results in the formation of one Sn-C-sp3 bond with the cleavage of one SnCAr bond as well as the W-C-sp3 bond to give novel heterodinuclear complexes Ar2SnCH-(3,5-Me(2)Pz)(2)(CO)(3)WX (X = Cl or Br), in which an intriguing (3)(K)-[N,Sn,N] coordination mode as well as an unsymmetrically semibridging carbonyl between the W-Sn bond is observed.