trans-[Ni(F){2-C5NHF3}(PEt3)2] | 196882-71-0

• 英文名称: trans-[Ni(F){2-C5NHF3}(PEt3)2]
• 英文别名: trans-Ni(PEt3)2(3,5,6-trifluropyrid-2-yl)F；trans-[NiF{2-C₅NF₃(4-H)}(PEt₃)₂]；trans-[Ni(F){2-C₅NHF₃}(PEt₃)₂]；trans-(PEt3)2NiF(3,5,6-C5HF3N)；trans-[NiF(2-C5NHF3)(PEt3)2]；cis-(PEt3)2NiF(3,5,6-C5HF3N)
• CAS: 196882-71-0；1357254-59-1
• 化学式: C₁₇H₃₁F₄NNiP₂
• 分子量: 446.071
• InChiKey: PLUVQKHSUXZOCQ-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：

  2,3,5,6-四氟吡啶 、 (PEt3)2Ni(η2-phenanthrene) 以 氘代甲苯 为溶剂， 生成 trans-[Ni(F){2-C5NHF3}(PEt3)2]
  参考文献：
  名称：

  Experimental Study of the Reaction of a Ni(PEt₃)₂Synthon with Polyfluorinated Pyridines: Concerted, Phosphine-Assisted, or Radical C–F Bond Activation Mechanisms?

  摘要：

  The mechanisms of the C F activation reactions of 2,3,5,6-tetrafluoropyridine and pentafluoropyridine with the phenanthrene adduct (PEt3)(2)Ni(eta(2)-C14H10) and Ni(PEt3)(4) as sources of (PEt3)(2)Ni were investigated. The activation of 2,3,5,6-tetrafluoropyridine proceeds via the mononuclear adduct (PEt3)(2)Ni(eta(2)-2,3,5,6-C5F4HN) (3) in equilibrium with the CH activation product, trans-(PEt3)(2)NiH(2,3,5,6-C5F4N) (2). The C-F activation reaction occurs by concerted oxidative addition, as judged by the observation of cis-(PEt3)(2)NiF(3,5,6-C5F3HN) (4), as an intermediate to trans-(PEt3)(2)NiF(3,5,6-C5F3HN) (1). The dinudear adduct [(PEt3)(2)Ni](2)(mu-eta(2):eta(2)-2,3,5,6-C5F4HN) (5) was not observed. Pentafluoropyridine reacted with the phenanthrene adduct (PEt3)(2)Ni(eta(2)-C14H10) to provide the mononuclear adduct (PEt3)(2)Ni(eta(2)-C5F5N) (6) and the dinuclear adduct [(PEt3)(2)Ni](2)-(mu-eta(2):eta(2)-C5F5N) (11). A (PEt3)(2)Ni adduct of the C-F activation product, (PEt3)(2)Ni[eta(2)-3,4,5,6-C5F4N-2-NiF(PEt3)(2)] (10), and the double C F activation product [trans-(PEt3)(2)NiF](2)(3,4,5-C5F3N) (9) were also assigned by NMR spectroscopy. Complex 10 was a precursor to both trans-(PEt3)(2)NiF(3,4,5,6-C5F4N) (7) and 9. The rate of formation of trans-(PEt3)(2)NiF(3,4,5,6-C5F4N) (7) is not first order with respect to the concentration of 6. The EPR spectrum of (PEt3)(2)Ni(eta(2)-C14H10) and pentafluoropyridine, in a toluene solution that was frozen in N-2(1) during reaction at -40 degrees C, revealed signals consistent with the speculative formulation (PEt3)(2)Ni(2-C5F4N). These results suggest that pathways other than concerted oxidative addition or phosphine-assisted pathways arising from 6 are required to account for the unusual selectivity of the C F activation of pentafluoropyridine by the (PEt3)(2)Ni fragment.

  DOI：

  10.1021/om200990g

文献信息

• Rapid Intermolecular Carbon−Fluorine Bond Activation of Pentafluoropyridine at Nickel(0):  Comparative Reactivity of Fluorinated Arene and Fluorinated Pyridine Derivatives
  作者：Leroy Cronin、Catherine L. Higgitt、Ralf Karch、Robin N. Perutz

  DOI：10.1021/om9705160

  日期：1997.10.1

  X-ray crystal structure reveals a molecular complex with approximately square-planar coordination at nickel, a Ni−F distance of 1.836(5) Å and a Ni−C distance of 1.878(7) Å. Analogous reactions with pentafluoropyridine and 2,3,5,6-tetrafluoropyridine proceed much faster. Both reactions yield C−F activation products analogous to 1 in which a single regioisomer is dominant. The crystal structure of t

  用Ni（COD）六氟苯反应2在三乙基膦镍（PET或与存在（COD = 1,5-，-cyclooctadiene）3）4在室温下导致非常缓慢形成的反式-Ni（PET 3）2（ C 6 F 5）F（1）。X射线晶体结构揭示了在镍，Ni-F距离为1.836（5），Ni-C距离为1.878（7）的情况下在镍上具有近似方形平面配位的分子配合物。与五氟吡啶和2,3,5,6-四氟吡啶的类似反应进行得更快。两个反应均产生类似于1的CF活化产物其中单一的区域异构体占主导地位。反式-Ni（PEt 3）2（C 5 HF 3 N）F（3）的晶体结构表明三氟吡啶基配体在2位金属化。Ni-F和Ni-C距离分别为1.856（2）和1.869（4）Å。在1和3的结构中，芳基环的平面垂直于镍配位平面。这些结构提供了在方形平面Ni（II）处镍-氟距离的第一个值。Ni（COD）2与PEt 3和3,5-dichloro-2,4,
• C–F Bond activation at Ni(0) and simple reactions of square planar Ni(ii) fluoride complexes
  作者：Suzanne Burling、Paul I. P. Elliott、Naser A. Jasim、Richard J. Lindup、Jennifer McKenna、Robin N. Perutz、Stephen J. Archibald、Adrian C. Whitwood

  DOI：10.1039/b510052f

  日期：——

  The reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with triethylphosphine and pentafluoropyridine in hexane has been shown previously to yield trans-[NiF(2-C5NF4)(PEt3)2] (1a) with a preference for reaction at the 2-position of the heteroaromatic. The corresponding reaction with 2,3,5,6-tetrafluoropyridine was shown to yield trans-[NiF(2-C5NF3H)(PEt3)2] (1b). In this paper, we show that reaction of Ni(COD)2 with triethylphosphine and pentafluoropyridine in THF yields a mixture of 1a and 1b. Competition reactions of Ni(COD)2 with triethylphosphine in the presence of mixtures of heteroaromatics in hexane reveal a kinetic preference of k(pentafluoropyridine) : k(2,3,5,6-tetrafluoropyridine) = 5.4 : 1. Treatment of 1a and 1b with Me3SiN3 affords trans-[Ni(N3)(2-C5NF4)(PEt3)2] (2a) and trans-[Ni(N3)(2-C5NHF3)(PEt3)2] (2b), respectively. The complex trans-[Ni(NCO)(2-C5NHF3)(PEt3)2] (3b) is obtained on reaction of 1b with Me3SiNCO and by photolysis of 2b under CO, while trans-[Ni(η1-CCPh)(2-C5NF4)(PEt3)2] (4a) is obtained by reaction of phenylacetylene with 1a. Addition of KCN, KI and NaOAc to complex 1a affords trans-[Ni(X)(2-C5NF4)(PEt3)2] (5a X = CN, 6a X = I, 7a X = OAc), respectively. The PEt3 groups of complex 1a are readily replaced by addition of 1,2-bis(dicyclohexylphosphino)ethane (dcpe) to produce [NiF(2-C5F4N)(dcpe)] (8a). Addition of dcpe to trans-[Ni(OTf)(2-C5F4N)(PEt3)2] (10a), however, yields the salt [Ni(2-C5F4N)(dcpe)(PEt3)](OTf) (9a) by substitution of only one PEt3 and displacement of the triflate ligand. The structures of 2b, 4a, 7a and 8a were determined by X-ray crystallography. The influence of different ancillary ligands on the bond lengths and angles of square-planar nickel structures with polyfluoropyridyl ligands is analysed.

  Ni(COD)2的反应 (COD = 1,5-环辛二烯) 与三乙基膦和五氟吡啶在己烷中的反应先前已被证明可产生反式-[NiF(2-C5NF4)(PEt3)2] (1a) 优选在杂芳族化合物的2-位上反应。与 2,3,5,6-四氟吡啶的相应反应显示产生反式-[NiF(2-C5NF3H)(PEt3)2] (1b)。在本文中，我们证明 Ni(COD)2 与三乙基膦和五氟吡啶在 THF 中反应生成 1a 和 1b 的混合物。 Ni(COD)2 与三乙基膦在己烷中杂芳族化合物混合物存在下的竞争反应揭示了 k(五氟吡啶) 的动力学偏好：k(2,3,5,6-四氟吡啶) = 5.4 : 1. 用 Me3SiN3 处理 1a 和 1b 得到反式-[Ni(N3)(2-C5NF4)(PEt3)2] (2a) 和反式-[Ni(N3)(2-C5NHF3)(PEt3)2] 分别为（2b）。配合物反式-[Ni(NCO)(2-C5NHF3)(PEt3)2] (3b) 是通过 1b 与 Me3SiNCO 反应并通过在 CO 下光解 2b 获得的，而反式-[Ni(β1-CCPh)(2-C5NF4)(PEt3)2] (4a)由苯乙炔与1a反应得到。将 KCN、KI 和 NaOAc 添加到配合物 1a 中得到反式-[Ni(X)(2-C5NF4)(PEt3)2] （5a X = CN，6a X = I，7a X = OAc）。配合物 1a 的 PEt3 基团很容易通过添加 1,2-双(二环己基膦基)乙烷 (dCPe) 进行替换，生成 [NiF(2-C5F4N)(dCPe)] (8a)。将 dCPe 添加到反式-[Ni(OTf)(2-C5F4N)(PEt3)2] 中 然而，(10a) 产生盐 [Ni(2-C5F4N)(dCPe)(PEt3)](OTf) (9a)仅取代一个PEt3并置换三氟甲磺酸酯配体。 2b、4a、7a和8a的结构通过X射线晶体学测定。分析了不同辅助配体对多氟吡啶配体的方形平面镍结构的键长和角度的影响。
• The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors
  作者：Dan A. Smith、Torsten Beweries、Clemens Blasius、Naseralla Jasim、Ruqia Nazir、Sadia Nazir、Craig C. Robertson、Adrian C. Whitwood、Christopher A. Hunter、Lee Brammer、Robin N. Perutz

  DOI：10.1021/jacs.5b07509

  日期：2015.9.16

  The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)(2)], R = Et la, Cy lb, trans-[Pd(F) (4-C5NF4) (PCy3)(2)](2), trans-[Pt(F)2-C5NF2H(CF3)}-(PCy3)(2)] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability beta (Hunter scale) for the group 10 metal fluorides is far greater (la 12.1, lb 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, Sa 4.7, 6a 4.7, 4b 6.9, Sb 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to la in carbon tetrachloride (-23.5 +/- 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of p pi-d pi- bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F)2-C5NF3(NH2)}(PEt3)(2)], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.