[Pd(2-(4'-tolylazo)-5-methylphenyl)(κ(1)-bis(diphenlphosphino)methane)(κ(2)-bis(diphenylphosphino)methane)]OSO2CF3 | 189197-86-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 偶氮苯
• 英文名称: [Pd(2-(4'-tolylazo)-5-methylphenyl)(κ(1)-bis(diphenlphosphino)methane)(κ(2)-bis(diphenylphosphino)methane)]OSO2CF3
• 英文别名: [Pd(MeC6H3N2C6H4Me)(η(1)-bis(diphenylphosphino)methane)(η(2)-bis(diphenylphosphino)methane)]OSO2CF3；[Pd(κ1-C-C6H3(N=NC6H4-Me-4')-2-Me-5)(κ1-bis(diphenylphosphino)methane)(κ2-bis(diphenylphosphino)methane)]CF3SO3；diphenylphosphanylmethyl(diphenyl)phosphane;(4-methylbenzene-6-id-1-yl)-(4-methylphenyl)diazene;palladium(2+);trifluoromethanesulfonate
• CAS: 189197-86-2
• 化学式: CF₃O₃S*C₆₄H₅₇N₂P₄Pd
• 分子量: 1233.56
• InChiKey: BXMJQBXKEREQNO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  14.99
• 重原子数：
  79
• 可旋转键数：
  14
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  90.3
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  [Pd(2-(4'-tolylazo)-5-methylphenyl)(κ(1)-bis(diphenlphosphino)methane)(κ(2)-bis(diphenylphosphino)methane)]OSO2CF3 、 p-叠氮甲苯 以 四氢呋喃 为溶剂， 以94%的产率得到[Pd(κ(2)-C6H3MeN2C6H4CH3-C,N')(κ(2)-Ph2PCH2P(=NC6H4Me-4)Ph2-P,N)]OSO2CF3
  参考文献：
  名称：

  Palladium(II) Complexes of Monoaryliminophosphorane Derivatives of 1,2-Bis(Diphenylphosphino)methane. Crystal Structure of [Pd{κ²-C₆H₃(NN−C₆H₄Me-4‘)-2- (C₆H₄Me-4‘‘)-5-C,N‘}{κ²-PPh₂CH₂P(NC₆H₄Me-4)Ph₂-P,N}]

  摘要：

  The complex [Pd(azoMe)(kappa(1)-dppm)(kappa(2)-dppm)]TfO (azoMe = 2-(4'-tolylazo)-5-methylphenyl, dppm = bis(diphenylphosphino)methane, TfO = CF3SO3) reacts at room temperature with aryl azides N3Ar to give, in moderate to high yields, iminophosphorane complexes [Pd(kappa(2-)azoMe-C,N'){kappa(2)-PPh2CH2P(=NAr)Ph-2-P,N}]TfO [Ar = C6H4R, R = H (1), MeO-2 (2a), Me-2 (2b), NO2-2 (2c), MeO-3 (3a), NO2-3 (3c), MeO-4 (4a), Me-4 (4b), NO2-4 (4c)]. In all cases, there is a linear correlation between delta(P) (ppm) of both phosphorus atoms and temperature T (degrees C) [delta(P-1) = delta(1)(0) + a(1)T; delta(P-2) = delta(2)(0) + a(2)T]. In the ortho-substituted complexes 2a-c and the nitro derivatives 3c and 4c, crossing of the two delta/T plots of each complex is not observed and the change in chemical shift with temperature is small or nil, /a(1)/, /a(2)/ = (0-12) x 10(-3) ppm/degrees C. In the other complexes, the gradient of one of the straight; lines is positive (a(1) approximate to 26 x 10(-3) ppm/degrees C) and that of the other is negative (a(2) approximate to -7.5 x 10(-3) ppm/degrees C). Both lines cross in the range 0-25 degrees C. 4b reacts with [Au(acac)PPh3] (1:2) to give [Pd(azoMe-C,N'){PPh2C(AuPPh3)(2)P(=NAr)Ph-2-P,N}] [Ar = Me-4 (5b)]. [Pd(azoMe-C,N')(kappa(2)-dppm)]TfO reacts with NaN3 to give [Pd-2(azoMe)2(C)(mu(2)-N-3)(mu(2)-dppm)(2)]TfO (6). The crystal structure of 4b is reported.

  DOI：

  10.1021/om980445k
• 作为产物：
  描述：

  bis(μ-chloro)bis(azotoluene-C2,N)dipalladium(II) 、 双二苯基膦甲烷 以 二氯甲烷 、 丙酮 为溶剂， 生成 [Pd(2-(4'-tolylazo)-5-methylphenyl)(κ(1)-bis(diphenlphosphino)methane)(κ(2)-bis(diphenylphosphino)methane)]OSO2CF3
  参考文献：
  名称：

  钯配合物中相互间反式膦和芳基配体的配位困难及其与重要偶联过程的关系。钯膦，三氟甲磺酸，高氯酸盐和Aquo-2-（芳基偶氮）芳基配合物的家族的合成和晶体结构

  摘要：

  [Pd（C 6 H 3 N NR-2，X-5）Cl] 2与膦的反应得到[Pd（C 6 H 3 N NTo-2，Me-5）Cl（L）] [To = C 6 H 4 Me-4，L = PEt 3（1a），PPh 2 Me（1b）]或反式-[Pd（C 6 H 3 N 2 To-2，Me-5）ClL 2 ]（L = PEt 3（2a），PPh 2 Me（2b），L 2 =双（二苯基膦基）甲烷= dppm（2c））或反式-[Pd（C 6 H 3 N 2 X-2，R-5）Cl（μ-dppm）] 2（X = Me，R = To（3a）; X = H，R = Ph（3b）），取决于试剂的摩尔比。Tl（OTf）（OTf = O 3 SCF 3），AgClO 4或AgSbF 6与1a，b，2a，2c或3a反应生成各种[Pd（C 6 H 3 N NTo-2，Me- 5）（Y）（L）]（L = PEt 3，Y =

  DOI：

  10.1021/om961094h

文献信息

• Mono- and di-nuclear complexes of ortho-palladated and -platinated 4,4′-dimethylazobenzene with bis(diphenylphosphino)methane. More data on transphobia
  作者：José Vicente、Aurelia Arcas、Delia Bautista、M.Carmen Ramı́rez de Arellano

  DOI：10.1016/s0022-328x(02)01729-1

  日期：2002.12

  Complexes [Pd(κ2-R)(μ-Cl)]2 [κ2-R=κ2-C,N′-C6H3(NNC6H4Me-4′)-2-Me-5 (1)] and [Pd(κ1-R)Cl(κ1-dppm)(κ2-dppm)]TfO [dppm=bis(diphenylphosphino)methane (2)] have been used to prepare new palladium derivatives containing dppm. Thus, complex 1 reacts with one equivalent of dppm to afford [Pd(κ2-R)Cl}2(μ-dppm)] (3) and with AgClO4 and dppm (1:2:2 molar ratios) to give [Pd(κ2-R)(κ2-dppm)]ClO4 (4·ClO4). The

  物[Pd（κ 2 -R）（μ-Cl）的] 2 [κ 2 -R =κ 2 - C，N' -C 6 ħ 3（NNC 6 ħ 4 Me-4 ' ）-2-我-5（1）]和[钯（κ 1 -R）氯（κ 1 -dppm）（κ 2 -dppm）] TFO [DPPM =双（二苯基膦基）甲烷（2）]已被用于制备新的钯含有dppm的衍生物。因此，复杂1种发生反应与一个当量的DPPM，得到[PD（κ 2 -R）氯} 2（μ-DPPM）]（3）中并用AgClO 4和DPPM（1：2：2分的摩尔比），得到[钯（κ 2 -R）（κ 2 -dppm）] CLO 4（4 · CLO 4）。此复合物（的三氟甲磺酸盐4 · TFO与PPH）反应3，得到[钯（κ 1 -R）（PPH 3）（κ 2 -dppm）] TFO（5）。双核配合物是通过使2（i）与[AuCl（PPh 3）]或[AuCl（tht）]（tht =四氢噻
• The Difficulty of Coordinating Mutually <i>trans</i> Phosphine and Aryl Ligands in Palladium Complexes and Its Relation to Important Coupling Processes. Syntheses and Crystal Structures of a Family of Palladium Phosphino, Triflato, Perchlorato, and Aquo-2-(arylazo)aryl Complexes
  作者：José Vicente、Aurelia Arcas、Delia Bautista、Peter G. Jones

  DOI：10.1021/om961094h

  日期：1997.5.1

  [Pd(C6H3NNTo-2,Me-5)(Y)(L)] (L = PEt3, Y = TfO (4a); L = PPh2Me, Y = TfO (4b), ClO4 (4b‘)), trans-[Pd(C6H3N2To-2,Me-5)(OTf)(PEt3)2] (5), [Pd(C6H3N2To-2,Me-5)(η1-dppm)(η2-dppm)]TfO (6), or [Pd(C6H3NNR-2,X-5)(η2-dppm)]Y (X = Me, R = To, Y = TfO (7a)). Complexes [Pd(C6H3NNR-2,X-5)(η2-dppm)]SbF6 (X = Me, R = To (7a‘); X = H, R = Ph (7b)) can be prepared by reacting [Pd(C6H3NNR-2,X-5)Cl]2 with AgSbF6 and dppm. Complex

  [Pd（C 6 H 3 N NR-2，X-5）Cl] 2与膦的反应得到[Pd（C 6 H 3 N NTo-2，Me-5）Cl（L）] [To = C 6 H 4 Me-4，L = PEt 3（1a），PPh 2 Me（1b）]或反式-[Pd（C 6 H 3 N 2 To-2，Me-5）ClL 2 ]（L = PEt 3（2a），PPh 2 Me（2b），L 2 =双（二苯基膦基）甲烷= dppm（2c））或反式-[Pd（C 6 H 3 N 2 X-2，R-5）Cl（μ-dppm）] 2（X = Me，R = To（3a）; X = H，R = Ph（3b）），取决于试剂的摩尔比。Tl（OTf）（OTf = O 3 SCF 3），AgClO 4或AgSbF 6与1a，b，2a，2c或3a反应生成各种[Pd（C 6 H 3 N NTo-2，Me- 5）（Y）（L）]（L = PEt 3，Y =
• Palladium(II) Complexes of Monoaryliminophosphorane Derivatives of 1,2-Bis(Diphenylphosphino)methane. Crystal Structure of [Pd{κ²-C₆H₃(NN−C₆H₄Me-4‘)-2- (C₆H₄Me-4‘‘)-5-<i>C</i>,<i>N</i>‘}{κ²-PPh₂CH₂P(NC₆H₄Me-4)Ph₂-<i>P</i>,<i>N</i>}]
  作者：José Vicente、Aurelia Arcas、Delia Bautista、M. Carmen Ramírez de Arellano

  DOI：10.1021/om980445k

  日期：1998.10.1

  The complex [Pd(azoMe)(kappa(1)-dppm)(kappa(2)-dppm)]TfO (azoMe = 2-(4'-tolylazo)-5-methylphenyl, dppm = bis(diphenylphosphino)methane, TfO = CF3SO3) reacts at room temperature with aryl azides N3Ar to give, in moderate to high yields, iminophosphorane complexes [Pd(kappa(2-)azoMe-C,N')kappa(2)-PPh2CH2P(=NAr)Ph-2-P,N}]TfO [Ar = C6H4R, R = H (1), MeO-2 (2a), Me-2 (2b), NO2-2 (2c), MeO-3 (3a), NO2-3 (3c), MeO-4 (4a), Me-4 (4b), NO2-4 (4c)]. In all cases, there is a linear correlation between delta(P) (ppm) of both phosphorus atoms and temperature T (degrees C) [delta(P-1) = delta(1)(0) + a(1)T; delta(P-2) = delta(2)(0) + a(2)T]. In the ortho-substituted complexes 2a-c and the nitro derivatives 3c and 4c, crossing of the two delta/T plots of each complex is not observed and the change in chemical shift with temperature is small or nil, /a(1)/, /a(2)/ = (0-12) x 10(-3) ppm/degrees C. In the other complexes, the gradient of one of the straight; lines is positive (a(1) approximate to 26 x 10(-3) ppm/degrees C) and that of the other is negative (a(2) approximate to -7.5 x 10(-3) ppm/degrees C). Both lines cross in the range 0-25 degrees C. 4b reacts with [Au(acac)PPh3] (1:2) to give [Pd(azoMe-C,N')PPh2C(AuPPh3)(2)P(=NAr)Ph-2-P,N}] [Ar = Me-4 (5b)]. [Pd(azoMe-C,N')(kappa(2)-dppm)]TfO reacts with NaN3 to give [Pd-2(azoMe)2(C)(mu(2)-N-3)(mu(2)-dppm)(2)]TfO (6). The crystal structure of 4b is reported.