[Pd(E-C6H(CH=CHPh)-6-(OMe3)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)]

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: [Pd(E-C6H(CH=CHPh)-6-(OMe3)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)]
• 英文别名: chloropalladium(1+);N,N,N',N'-tetramethylethane-1,2-diamine;1,2,3-trimethoxy-5-[(E)-2-phenylethenyl]benzene-6-ide
• 化学式: C₂₃H₃₃ClN₂O₃Pd
• 分子量: 527.4
• InChiKey: KLXOKJOIYDJOIW-WCVSPGPUSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.48
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  34.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-丁炔 、 [Pd(E-C6H(CH=CHPh)-6-(OMe3)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)] 、 三氟甲磺酸铊 以 二氯甲烷 为溶剂， 以77%的产率得到[Pd(η-(C9H(CH2C6H5)-1-(Me)2-2,3-(OMe)3-5,6,7))(N,N,N',N'-tetramethylethylenediamine)]triflate
  参考文献：
  名称：

  Palladium-Assisted Formation of Carbon−Carbon Bonds. 9. Synthesis of (2-Alkenylaryl)- and Indenylpalladium Complexes

  摘要：

  (o-Formylaryl)palladium complexes. [Pd{C6H(CHO)-6-R-3-2,3,4)X(N-N)] [R = OMe; X = Cl; N-N = bpy (2,2'-bipyridine) (la), tmeda (N,N,N',N'-tetramethylethylenediamine) (Ib). R = H; X = Br; N-N = bpy (2a), tmeda (2b)] react with ylides PhCH=PPh3, pyCH=PPh3 (PY = 2-pyridyl), or ClCH=PPh3 to give the (o-alkenylaryl)palladium derivatives [Pd{C6HCH=CHPh-6-(OMe)(3)-2,3,4)Cl(N-N)] [N-N = bpy (3a), N-N = tmeda (3b)], [Pd{C6HCH= CHpy-6-(OMe)(3)-2,3,4}Cl(N-N)] [N-N = bpy (4)], [Pd{C6H(E-CH=CHCl)-6-(OMe)(3)-2,3,4}-Cl(tmeda)] (5), or [Pd(C6H4CH=CHPh-2)Br(N-N)] [N-N = bpy (6a), N-N = tmeda (6b)], The compounds 3a, 4, and 6a,b are obtained as mixtures off and Z isomers, whereas the formation of 3b and 5 is stereoselective (E isomer). The reaction of the (o-acetylaryl)palladium complexes [Pd{C6HC(O)Me-6-(OMe)(3)-2,3,4}Cl(tmeda)] (7) and [Pd{C6H4(C(O)Me)-2}Br(bpy)] (8) with bases results in the formation of the 3-palladaindan-1-ones [Pd(kappa (2)-{C6HC(O)CH2-6-(OMe)(3)-2,3,4})(tmeda)] (9) and [Pd(kappa (2)-{C6H4C(O)CH2-2)(bpy)] (10). Complexes 3b and 6a,b react with alkynes-RC=CR' to give indenylpalladium complexes [Pd{eta -C9HBn-1-R-2-R'-3-(OMe)(3)-5,6,7}(tmeda)]TfO [Bn = benzyl, TfO = CF3SO3, R = R' = Me(11); R = C(O)Me, R' = H (12)] and [Pd{eta -C9H4Bn-1-R-2-R'-3}(N-N)]TfO [R = R' = H, N-N = bpy (13a), tmeda (13b); R = R' = Me, N-N = bpy (14a), tmeda (14b); R = R' = Et, N-N = bpy (15a), tmeda (15b); R = R' = Ph, N-N bpy (16a), tmeda (16b); R = Ph, R' = H and R = H, R' = Ph, N-N = bpy (17a); R = H, R' = Ph, N-N = tmeda (17b); R = Ph, R' = Me, N-N = bpy (18a), N-N = tmeda (18b)]. Complex 3b reacts with Me2C=C=CH2, CS2, or MeN=C=S to give [Pd(eta (3)-CMe2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4}CH2)(tmeda)]TfO (19), [Pd(S2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (20), or [Pd(SC(NMe)(C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (21). The crystal structures of 12, 17b, and 18a have been determined; the hapticities of the indenyl five-membered rings are intermediate between eta (3) and eta (5).

  DOI：

  10.1021/om000370w
• 作为产物：
  描述：

  bis-(6-formyl-{2,3,4-trimethoxymethylphenyl})mercury(II) 在 t-BuOK 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 生成 [Pd(E-C6H(CH=CHPh)-6-(OMe3)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)]
  参考文献：
  名称：

  Palladium-Assisted Formation of Carbon−Carbon Bonds. 9. Synthesis of (2-Alkenylaryl)- and Indenylpalladium Complexes

  摘要：

  (o-Formylaryl)palladium complexes. [Pd{C6H(CHO)-6-R-3-2,3,4)X(N-N)] [R = OMe; X = Cl; N-N = bpy (2,2'-bipyridine) (la), tmeda (N,N,N',N'-tetramethylethylenediamine) (Ib). R = H; X = Br; N-N = bpy (2a), tmeda (2b)] react with ylides PhCH=PPh3, pyCH=PPh3 (PY = 2-pyridyl), or ClCH=PPh3 to give the (o-alkenylaryl)palladium derivatives [Pd{C6HCH=CHPh-6-(OMe)(3)-2,3,4)Cl(N-N)] [N-N = bpy (3a), N-N = tmeda (3b)], [Pd{C6HCH= CHpy-6-(OMe)(3)-2,3,4}Cl(N-N)] [N-N = bpy (4)], [Pd{C6H(E-CH=CHCl)-6-(OMe)(3)-2,3,4}-Cl(tmeda)] (5), or [Pd(C6H4CH=CHPh-2)Br(N-N)] [N-N = bpy (6a), N-N = tmeda (6b)], The compounds 3a, 4, and 6a,b are obtained as mixtures off and Z isomers, whereas the formation of 3b and 5 is stereoselective (E isomer). The reaction of the (o-acetylaryl)palladium complexes [Pd{C6HC(O)Me-6-(OMe)(3)-2,3,4}Cl(tmeda)] (7) and [Pd{C6H4(C(O)Me)-2}Br(bpy)] (8) with bases results in the formation of the 3-palladaindan-1-ones [Pd(kappa (2)-{C6HC(O)CH2-6-(OMe)(3)-2,3,4})(tmeda)] (9) and [Pd(kappa (2)-{C6H4C(O)CH2-2)(bpy)] (10). Complexes 3b and 6a,b react with alkynes-RC=CR' to give indenylpalladium complexes [Pd{eta -C9HBn-1-R-2-R'-3-(OMe)(3)-5,6,7}(tmeda)]TfO [Bn = benzyl, TfO = CF3SO3, R = R' = Me(11); R = C(O)Me, R' = H (12)] and [Pd{eta -C9H4Bn-1-R-2-R'-3}(N-N)]TfO [R = R' = H, N-N = bpy (13a), tmeda (13b); R = R' = Me, N-N = bpy (14a), tmeda (14b); R = R' = Et, N-N = bpy (15a), tmeda (15b); R = R' = Ph, N-N bpy (16a), tmeda (16b); R = Ph, R' = H and R = H, R' = Ph, N-N = bpy (17a); R = H, R' = Ph, N-N = tmeda (17b); R = Ph, R' = Me, N-N = bpy (18a), N-N = tmeda (18b)]. Complex 3b reacts with Me2C=C=CH2, CS2, or MeN=C=S to give [Pd(eta (3)-CMe2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4}CH2)(tmeda)]TfO (19), [Pd(S2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (20), or [Pd(SC(NMe)(C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (21). The crystal structures of 12, 17b, and 18a have been determined; the hapticities of the indenyl five-membered rings are intermediate between eta (3) and eta (5).

  DOI：

  10.1021/om000370w

文献信息

• Palladium-Assisted Formation of Carbon−Carbon Bonds. 5.¹ Reactions of (<i>o</i>-Styrylaryl)palladium Complexes with Alkynes. Synthesis of Palladium Complexes with Highly Functionalized Indenyl Ligands. Crystal and Molecular Structures of (1-Benzyl-2,3-diphenyl-5,6,7-trimethoxyindenyl)- and (1-Benzyl-3-phenyl-5,6,7-trimethoxyindenyl)palladium(II) Complexes
  作者：José Vicente、José-Antonio Abad、Ralph Bergs、Peter G. Jones、M. Carmen Ramírez de Arellano

  DOI：10.1021/om950847h

  日期：1996.3.5

  7-trimethoxyindenyl (4)]. When a mixture of [Pd(E-R)Cl(bipy)] (bipy = 2,2‘-bipyridine) and [Pd(Z-R)Cl(bipy)] is reacted with Tl(CF3SO3) and MeC⋮CMe, the complex [Pd(η-Ind)(bipy)]CF3SO3 [1-benzyl-2,3-dimethyl-5,6,7-trimethoxyindenyl (5)] is obtained. The structures of 3 and 4 have been determined by X-ray studies at 203 and 173 K, respectively. According to the structural data for 3 and 4, the hapticity of the

  [Pd（E- R）Cl（tmeda）]的反应[R = C 6 H（E -CH CHPh）-6-（OMe）3 -2,3,4; tmeda = N，N，N '，N'-四甲基乙二胺]与Tl（CF 3 SO 3）和CH⋮CH，PhC⋮CPh或PhC⋮CH选择性生成化合物[Pd（η-Ind）（tmeda）] CF 3 SO 3 [Ind ＝ 1-苄基-5,6,7-三甲氧基茚基（2），1-苄基-2,3-二苯基-5,6,7-三甲氧基茚基（3），1-苄基-3-苯基- 5,6,7-三甲氧基茚基（4）]。当[Pd（E-R）Cl（bipy）]（bipy = 2,2'-bipyridine）和[Pd（Z -R）Cl（bipy）]与Tl（CF 3 SO 3）和MeC⋮CMe反应，形成复合物[Pd得到（η-Ind）（Bipy）] CF 3 SO 3 [1-苄基-2,3-二甲基-5,6,7-三甲氧基茚基（5）]。3和4的结构已分别通过X射线研究在203
• The first ligand-assisted stereoselective Wittig reactions. Synthesis and crystal structure of the 3-palladaindan-1-one, [Pd{C6H[C(O)CH2]-6-(OMe)3-2,3,4}(Me2NCH2CH2NMe2)]
  作者：Jos� Vicente、Jos�-Antonio Abad、Ralph Bergs、Peter G. Jones、Delia Bautista

  DOI：10.1039/dt9950003093

  日期：——

  Reactions of [Pd(R(H))Cl(L-L)] [R(H) = C6H(CHO)-6-(OMe)(3)-2,3,4] with Ph(3)P=CHR (R = Ph or 2-pyridyl) gave mixtures of the isomeric compounds [Pd(E-R')Cl(L-L)] and [Pd(Z-R')Cl(L-L)] [R' = C6H(CH=CHPh)-6-(OMe)(3)-2,3,4 or C6HCH=CH(C5H5N-2)}-6-(OMe)(3)-2,3,4] when L-L = 2,2'-bipyridine or only the corresponding E isomers when L-L = N,N,N',N'-tetramethylethylenediamine; however, the complex [Pd(R(Me))C\(tmeda)] [R(Me) = C6HC(O)Me}-6-(OMe)(3)-2,3,4] reacts with Ph(3)P=CHPh to give [PdC6H[C(O)CH2]-6-(OMe)(3)-2,3,4}(tmeda)].