bis(η3-allyl)nickel triphenylphosphine | 74951-18-1

• 英文名称: bis(η3-allyl)nickel triphenylphosphine
• 英文别名: (η3-allyl)2Ni(PPh3)
• CAS: 74951-18-1
• 化学式: C₂₄H₂₅NiP
• 分子量: 403.126
• InChiKey: QQBVSULJMMVFFA-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  bis(η3-allyl)nickel triphenylphosphine 以 氘代甲苯 为溶剂， 生成 (1,2,5,6-η1,5-hexadiene)nickel triphenylphosphine
  参考文献：
  名称：

  过渡金属烯丙基：IV。的（η 3 -烯丙基）2个中号络合物镍，钯和铂的：与叔膦反应

  摘要：

  一系列的1：1个加合物已制备通过处理双- η 3 -烯丙基镍，钯和铂与叔膦的络合物。在晶体它们在溶液中的结构以及研究已显示，既18电子（η 3 -烯丙基）2 ML络合物以及16电子（η 1 -烯丙基） - （η 3 -烯丙基）M可能会形成L复合物。

  DOI：

  10.1016/s0022-328x(00)81073-6
• 作为产物：
  描述：

  bis(η3-allyl)nickel(II) 在 triphenylphosphine 作用下， 以 正戊烷 为溶剂， 以78.4%的产率得到bis(η3-allyl)nickel triphenylphosphine
  参考文献：
  名称：

  过渡金属烯丙基：IV。的（η 3 -烯丙基）2个中号络合物镍，钯和铂的：与叔膦反应

  摘要：

  一系列的1：1个加合物已制备通过处理双- η 3 -烯丙基镍，钯和铂与叔膦的络合物。在晶体它们在溶液中的结构以及研究已显示，既18电子（η 3 -烯丙基）2 ML络合物以及16电子（η 1 -烯丙基） - （η 3 -烯丙基）M可能会形成L复合物。

  DOI：

  10.1016/s0022-328x(00)81073-6

文献信息

• Synthesis, Properties, and Reactivity with Carbon Dioxide of (allyl)₂Ni(L) Complexes
  作者：Jianguo Wu、Nilay Hazari、Christopher D. Incarvito

  DOI：10.1021/om2002238

  日期：2011.6.13

  A family of nickel allyl complexes of the type (allyl)(2)Ni(L) (L = PMe3 (1), PEt3 (2), PPh3 (3), NHC (4); NHC = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-2H-imidazol-2-ylidene) and (2-methylallyl)(2)Ni(L) (L = PMe3 (5), PEt3 (6), PPh3 (7), NHC (8)) have been prepared using literature methods. Compounds 5, 7, and 8 were characterized by X-ray crystallography. Whereas compounds 5 and 7 are 18-electron species with two eta(3)-allyl ligands, the NHC-supported complexes are 16-electron species with one eta(1)- and one eta(3)-allyl ligand. Using DFT we have identified the key factors in predicting whether complexes of the type (allyl)(2)M(L) (M = Ni, Pd) are 16- or 18-electron species. Compounds 1, 2, and 5-8 readily decompose to give a mixture of products, while compound 4 decomposes to give the unusual Ni-0 species (eta(4)-1,5-hexadiene)Ni(NHC) (9), which was characterized by X-ray crystallography. The reactions of 1-8 with CO2 were investigated. Compounds 5-8 react rapidly with CO2 at low temperature to form well-defined unidentate nickel carboxylates of the type (eta(3)-2-methylallyl)Ni(OC(O)C4H7)(L) (L = PMe3 (10), PEt3 (11), PPh3 (12), NHC (13)). The structure of 13 was elucidated using X-ray crystallography. In contrast, compounds 1-4 do not react with CO2. We believe that the difference in reactivity between the 2-methylallyl-supported complexes and the allyl-supported complexes is related to the mechanism of CO2 insertion.