(η3-2-methylallyl)(η1-OC(O)CH2C(CH2)CH3)Ni(PEt3) | 1308260-00-5

• 英文名称: (η3-2-methylallyl)(η1-OC(O)CH2C(CH2)CH3)Ni(PEt3)
• CAS: 1308260-00-5
• 化学式: C₁₅H₂₉NiO₂P
• 分子量: 331.058
• InChiKey: KVJOWJKUBSJKJR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  bis(η3-2-methylallyl)nickel 、 二氧化碳 、 三乙基膦 以 甲苯 为溶剂， 以97.5%的产率得到(η3-2-methylallyl)(η1-OC(O)CH2C(CH2)CH3)Ni(PEt3)
  参考文献：
  名称：

  Synthesis, Properties, and Reactivity with Carbon Dioxide of (allyl)₂Ni(L) Complexes

  摘要：

  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.

  DOI：

  10.1021/om2002238