[N(o-C6H4PCy2)2]NiCl | 881020-86-6

• 英文名称: [N(o-C6H4PCy2)2]NiCl
• 英文别名: [Cy-PNP]NiCl
• CAS: 881020-86-6
• 化学式: C₃₆H₅₂ClNNiP₂
• 分子量: 654.906
• InChiKey: KXKKXBNYNHGBRE-UHFFFAOYSA-M

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：

  [N(o-C6H4PCy2)2]NiCl 在 Al(CH₃)3 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 [N(o-C6H4PCy2)2]NiPh
  参考文献：
  名称：

  Intermolecular Arene C−H Activation by Nickel(II)

  摘要：

  Intermolecular arene C-H activation mediated by a divalent nickel species under extremely mild conditions is described. The reactions of either Ni(COD)2 with H[N(o-C6H4PR2)2] (H[R-PNP]; R = iPr, Cy) in benzene at room temperature or [R-PNP]NiCl with LiBHEt3 in THF at -35 degrees C produced the corresponding [R-PNP]NiH in high yield. Addition of 1 equiv of B(C6F5)3 to a benzene solution of [R-PNP]NiH at room temperature led to the formation of a mixture that contains [R-PNP]NiPh and [R-PNP]Ni(C6F5), both of which are proposed to evolve from zwitterionic [R-PNP]Ni(mu-H)B(C6F5)3. In contrast, the reaction of [R-PNP]NiH with AlMe3 in benzene at room temperature afforded exclusively the corresponding [R-PNP]NiPh. Similar results were also observed for intermolecular toluene and m-xylene C-H activation by [R-PNP]NiH. A parallel study involving [R-PNP]NiMe (R = Ph, iPr, Cy) on the reactivity of intermolecular arene activation reveals the significance of pi basicity of Ni(II) in these molecules. The remarkable reactivity of inexpensive Ni(II) species established in this study is attractive, particularly from an economic viewpoint, as compared to the current alternatives of 4d and 5d metals.

  DOI：

  10.1021/ja065505p
• 作为产物：
  描述：

  氯化镍二甲氧基乙烷 、 [N(o-C6H4PCy2)2]Li(THF) 以 四氢呋喃 为溶剂， 以85%的产率得到[N(o-C6H4PCy2)2]NiCl
  参考文献：
  名称：

  镍（II）的酰胺夹钳配合物：合成，结构和反应性。

  摘要：

  三齿氨基二膦配体[N（o -C 6 H 4 PR 2）2 ] -（[R-PNP] -； R = Ph，iPr，Cy）已被制备并表征。H [Ph-PNP]，H [ i的去质子PR-PNP]和H [CY-PNP]与Ñ正丁基锂在-35醚溶液℃下制造的锂配合物[PH-PNP]李（THF）2，[我Pr-PNP] Li（solv）（solv = THF，Et 2 O）和[Cy-PNP] Li（solv）（solv = THF，Et 2 O）。[R-PNP] Li（solv）n与NiCl 2（DME）在-35°C的THF中反应生成[R-PNP] NiCl，然后使其与多种格氏试剂反应，得到相应的烃基配合物[R-PNP] NiR'（R = Ph，R'= Me，Et，n- Bu，i- Bu，n- hexyl，CH 2 SiMe 3，Ph; R = iPr，R'= Me，Et，n -Bu; R = Cy，R'=

  DOI：

  10.1021/om050943a

文献信息

• Terminal nickel(ii) amide, alkoxide, and thiolate complexes containing amido diphosphine ligands of the type [N(o-C6H4PR2)2]− (R = Ph, iPr, Cy)
  作者：Lan-Chang Liang、Pin-Shu Chien、Pei-Ying Lee、Jia-Ming Lin、Yu-Lun Huang

  DOI：10.1039/b719894a

  日期：——

  A series of nickel(ii) complexes of the type [R-PNP]Ni(ER') ([R-PNP](-) = [N(o-C(6)H(4)PR(2))(2)](-); R = Ph, (i)Pr, Cy; E = NH, O, S; R' = Ph, (t)Bu) featuring unsupported, covalently bound pi-donor ligands have been prepared and characterized. The metathetical reactions of [R-PNP]NiCl (R = Ph, (i)Pr, Cy) with LiNHPh, NaOPh, or NaSPh, respectively, produced the corresponding anilide [R-PNP]Ni(NHPh)

  [R-PNP] Ni（ER'）类型的一系列镍（ii）配合物（[R-PNP]（-）= [N（oC（6）H（4）PR（2））（2） ]（-）； R ＝ Ph，（i）Pr，Cy； E ＝ NH，O，S； R′＝ Ph，（t）Bu），其特征是未支撑的，共价结合的π-供体配体。[R-PNP] NiCl（R = Ph，（i）Pr，Cy）与LiNHPh，NaOPh或NaSPh的易位反应产生了相应的苯胺基[R-PNP] Ni（NHPh），酚盐[R- PNP] Ni（OPh）和硫酚盐[R-PNP] Ni（SPh）衍生物。用LiNH（t）Bu或NaO（t）Bu处理[Ph-PNP] NiCl生成的叔丁基酰胺[Ph-PNP] Ni（NH（t）Bu）和叔丁氧化物[Ph-PNP] Ni（ O（t）Bu）。相反，制备[（i）Pr-PNP]（-）或[Cy-PNP]（-）的叔丁基酰胺和叔丁氧化物配合物的尝试没有成功。这些镍