dichloronickel(1+);1-[3-[(dimethylamino)methyl]-5-trimethylsilylbenzene-2-id-1-yl]-N,N-dimethylmethanamine | 320573-49-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dichloronickel(1+);1-[3-[(dimethylamino)methyl]-5-trimethylsilylbenzene-2-id-1-yl]-N,N-dimethylmethanamine
• CAS: 320573-49-7
• 化学式: C₁₅H₂₇Cl₂N₂NiSi
• 分子量: 393.074
• InChiKey: OBLKTTZZYQBYOI-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  在 CCl₄ 作用下， 以 四氯化碳 为溶剂， 生成 dichloronickel(1+);1-[3-[(dimethylamino)methyl]-5-trimethylsilylbenzene-2-id-1-yl]-N,N-dimethylmethanamine
  参考文献：
  名称：

  碳硅烷负载的芳镍（II）催化剂在均相催化中的“树突效应”：原子转移自由基加成中活性位点邻近效应的观察。

  摘要：

  均相和非均相催化剂的优势结合在金属树枝状分子中，其中镍基催化剂与碳硅烷树状大分子结合。描述了氧化还原催化行为中“树状效应”的第一个直接指示：树状聚合物载体的变化控制Ni（II）中心的接近度，进而控制催化活性。通过Ni（II）中心的较大分离可以避免由于Ni（III）形成而引起的催化剂失活（见图）。

  DOI：

  10.1002/(sici)1521-3773(20000103)39:1<176::aid-anie176>3.0.co;2-3

文献信息

• A “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts:  Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition
  作者：Arjan W. Kleij、Robert A. Gossage、Robertus J. M. Klein Gebbink、Nils Brinkmann、Ed J. Reijerse、Udo Kragl、Martin Lutz、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/ja0026612

  日期：2000.12.1

  Transmetalation of polylithiated, carbosilane (CS) dendrimers functionalized with the potentially terdentate ligand [C6H2(CH2NMe2)(2)-2,6-R-4](-) ( NCN) with NiCl2(PEt3)(2) produced a series of nickel-containing dendrimers [GO]-N-4 (4), [G1]-Ni-12 (5), and [G2]-Ni-36 (7) in moderate to good yields. The metallodendrimers 4, 5, and 7 are catalytically active in the atom-transfer radical addition (ATRA) reaction (Kharasch addition reaction), viz. the 1:1 addition of CCl4 to methyl methacrylate (MMA). The catalytic data were compared to those obtained for the respective mononuclear compound [NiCl(C6H2CH2NMe2}(2)-2,6-SiMe3-4)] (2). This comparison indicates a fast deactivation for the dendrimer catalysts beyond generation [GO]. The deactivation of [G1]-Ni-12 (5) and [G2]-Ni-36 (7) is caused by irreversible formation of catalytically inactive Ni(III) sites on the periphery of these dendrimers. This hypothesis is supported by results of model studies as well as ESR spectroscopic investigations. Interestingly, the use of two alternative nickelated [G1] dendrimers [G1]*-Ni-12 (11) and [G1]-Ni-8 (15), respectively, in which the distance between the Ni sites is increased, leads to significantly improved catalytic efficiencies which approximate those of the parent derivative 2 and [GO]-Ni-4 (4). Preliminary membrane catalysis experiments with [GO]-Ni-4 (4) and [G1]-Ni-12 (5) show that 5 can be efficiently retained in a membrane reactor system. The X-ray crystal structure of the Ni(III) complex [NiCl2(C6H2CH2NMe2}(2)-2,6-SiMe3-4)] (16), obtained from the reaction of 2 with CCl4, is also reported.