N,N,N',N'-tetramethylethylene diamine palladium(II) iodide | 86272-80-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N,N',N'-tetramethylethylene diamine palladium(II) iodide
• 英文别名: [PdI₂(N,N,N′,N′-tetramethylethylenediamine)]；[PdI₂(tmeda)]；[Pd(tmeda)I₂]；[Pd(N,N,N',N'-tetramethyethylendiamine)I₂]；[[PdI2(N,N,N',N'-tetramethylethylenediamine)]；diiodopalladium;N,N,N',N'-tetramethylethane-1,2-diamine
• CAS: 86272-80-2
• 化学式: C₆H₁₆I₂N₂Pd
• 分子量: 476.435
• InChiKey: XEVNQYPBWZSZBS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.88
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  silver nitrate 、 N,N,N',N'-tetramethylethylene diamine palladium(II) iodide 以 水 为溶剂， 以0.59 g的产率得到bis(nitrato)(N,N,N',N'-tetramethylethylenediamine)palladium(II)
  参考文献：
  名称：

  用于胆汁酸封装和传感的金属有机笼式受体

  摘要：

  开发合成超分子受体来溶解、清除、识别、封装和感知类固醇具有挑战性。尽管与类固醇具有亲和力的受体数量有限，但没有一种受体能够选择性地结合类固醇胆汁酸。在此，我们报告了一个C 2对称金属有机笼[Pd 6 L2 4 ] 12+和藤田笼的扩展版本[Pd 6 L1 4 ] 12+ ，由构象灵活的配体L2构建，通过配位访问驱动自组装。我们检查了两个笼子在水中的类固醇识别：两者都有某些共同的特征和独特的特征。 [Pd 6 L1 4 ] 12+通过形成 1:1 复合物结合疏水性胆汁酸和其他类固醇。相比之下，扩展的[Pd 6 L2 4 ] 12+笼表现出对两亲性胆汁酸和选择性类固醇的亲和力，将它们封装为二聚体，这是由合作的客体间氢键促进的。与[Pd 6 L1 4 ] 12+相比，[Pd 6 L2 4 ] 12+对胆酸的溶解增强能力强5倍。此外，扩展的[Pd 6 L2 4 ] 12+笼可以通过采用磺基罗丹明1

  DOI：

  10.1021/acs.inorgchem.4c00934
• 作为产物：
  描述：

  [Pd(C(O)C6H4NHC(O)NH(C6H4Me-4)-2)I(tmeda)] 以 氘代氯仿 为溶剂， 生成 N,N,N',N'-tetramethylethylene diamine palladium(II) iodide
  参考文献：
  名称：

  Synthesis and Reactivity of Ortho-Palladated Arylureas. Synthesis and Catalytic Activity of a C,N,C Pincer Complex. Stoichiometric Syntheses of Some N-Heterocycles

  摘要：

  1-(2-lodophenyl)-3-p-tolylurea (1) reacts with Pd(dba)(2) ([Pd-2(dba)(3)]-dba; dba = dibenzylideneacetone) in the presence of the appropriate ligands to give the ortho-palladated arylureas [Pd{C6H4NHC(O)NHTo-2}IL2] (To = C6H4Me-4; L-2 = tbubpy (4,4'-di-tert-butyl-2,2'-bipyridine) (2a), tmeda (N,N,N ',N '-tetramethylethylenediamine) (2b); L = PPh3 (2c)). Reaction of 2b with Tl(TfO) TfO = triflate, CF3SO3) results in the formation of cyclopalladated [Pd{kappa C-2,O- C6H4NHC(O)NHTo-2}(tmeda)]OTf (3b). The latter reacts with PPh3 to yield [Pd{C6H4NHC-(O)NHTo-2}(tmeda)(PPh3)]OTf (4b). Treatment of 2b with CO gives the corresponding acyl derivative [Pd{C(O)C6H4NHC(O)NHTo-2}I(tmeda)] (5b). If Tl(TfO) is added after the bubbling of CO, the C,N coupling product 3-p-tolyl-1H-quinazoline-2,4-dione (6) is formed. Complex 5b reacts with XyNC (Xy = 2,6-dimethylphenyl) to yield trans- [Pd{C(O)C6H4NHC-(O)NHTo-2}I(CNXy)(2)] (7). Both 5b and 7 decompose in solution to give 6. Complex 2b reacts with isocyanides to give the iminoacyl derivatives trans-[Pd{C(=NR)C6H4NHC(O)NHTo-2}I(CNR)2] (R = Xy (8x), Bu-t (8t)). The complex 8x gives the C,N coupling product 4-(xylylimino)-3-p-tolyl-3,4-dihydro-1H-quinazolin-2-one (9) after treatment with TlOTf 8x also reacts with bases (K2CO3 and Tl2CO3) to yield the iminoacyl amido carbene C,N,C pincer palladium complex [Pd{kappa C-3,N,C-C(=NXy)C6H4NC(O)NToC(NHXy)-2}(CNXy)] (10); this complex is an active precatalyst in Heck and Suzuki reactions. The reaction of 2b with R'C equivalent to CR" and TIOTf gives [Pd{kappa C-2,N-CR'=CR"C6H4NHC(O)NHTo-2}(tmeda)]OTf (R' = R" = Et (11be), CO2Me (11bm), Ph (11bp); R' = Ph, R" = CO2Me (11bq)). These complexes decompose in solution, and in the case of 11bp, 2,3-diphenylindole-l-carboxylic acid p-tolylamide (12p) was isolated. 11bq reacts with PPh3 to give 3-phenyl-1H-indole-2carboxylic acid methyl ester (13q). 11bp and 11bq decompose in the presence of CO to yield 3,4-diphenyl-2-quinolone (14po) and 2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qo), respectively. Similarly, when 11bq is reacted with XyNC, the C,N coupling compound 2-xylyl-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qnx) is formed. The crystal and molecular structures of 3b, 10-0.5CDCl(3), 11bp-OEt2, 11bq, and 14po have been determined.

  DOI：

  10.1021/om050451y

文献信息

• Reactivity of Ortho-Palladated Phenol Derivatives with Unsaturated Molecules. 1. Insertion of CO, Isocyanides, Alkenes, and Alkynes. CO/Alkene, Alkyne/Isocyanide, and Isocyanide/Alkene Sequential Insertion Reactions
  作者：José Vicente、José-Antonio Abad、Walter Förtsch、María-José López-Sáez、Peter G. Jones

  DOI：10.1021/om0496131

  日期：2004.9.1

  ]TfO (7aXy), which is the result of the successive insertion of an alkyne and an isocyanide into a palladium−carbon bond. The reaction of 4a with a 4-fold excess of isocyanide gives dimethyl 2-(2,6-dimethylphenyl)imino-2H-chromene-3,4-dicarboxylate iminecoumarin (8), a result of the sequential insertion of alkyne and isonitrile into the Pd−C bond, followed by a depalladation process, as the only characterizable

  HOC 6 H 4 I-2与[Pd 2（dba）3 ]·dba（“ Pd（dba）2 ”； dba =二亚苄基丙酮）和N-给体配体（4,4'-二叔丁基- 2,2'-联吡啶（dtbbpy），N，N，N- 'N '四甲基乙二胺（TMEDA），1,10-菲咯啉（phen）的）导致的芳基钯配合物[钯（C 6 H ^ 4 OH-2） I（L 2）]（L 2 = dtbbpy（1a '），tmeda（1a ''），phen（1a '））。配合物1a '和1a''与CO反应生成芳酰基衍生物[Pd C（O）C 6 H 4 OH-2} I（dtbbpy）]（2a '）和[Pd C（O）C 6 H 4 OH-2} I（tmeda）]（2a ''）。化合物1a '与异氰酸酯RNC反应（R = 2,6-二甲基苯基（Xy），tBU），得到[钯C（NR）C 6 H ^ 4 OH-2} I（dtbbpy）]（R =
• Synthesis, Molecular Structures, and Dynamics of Primary and Secondary Fluoroalkyl Complexes of Palladium(II) with Tetramethylethylenediamine (TMEDA) Ligands. Evaluation of the Structural <i>trans</i>-Influences of Methyl and Fluoroalkyl Groups as Ligands within the Same Coordination Sphere
  作者：Russell P. Hughes、Jason S. Overby、Alex Williamson、Kin-Chung Lam、Thomas E. Concolino、Arnold L. Rheingold

  DOI：10.1021/om000694k

  日期：2000.11.1

  principal steric effect of the perfluoroisopropyl group in the solid state is to generate an almost planar TMEDA ring. The solution NMR data for 1, 2, 4, 5, and 8 show resonances due to diastereotopic CF2 groups below room temperature, with the CF2 group acting as a remote sensor for formation of a stereocenter at the metal due to slowing of the inversion of the puckered five-membered metallacycle formed

  （TMEDA）Pd（CH 3）2（TMEDA =四甲基乙二胺）与伯全氟烷基碘的反应产生的产物混合物明显取决于溶剂的选择。在己烷中，（TMEDA）PdMe（R F）[R F＝n -C 3 F 7（1）；n＝1。以约50％的产率提供n -C 4 F 9（2）]，同时形成（TMEDA）Pd（CH 3）I（3）。在己烷中3从溶液中沉淀出来，不会进一步反应，但会以THF为溶剂3保留在溶液中，并在有光的情况下与R F I反应，得到（TMEDA）PdI（R F）[R F = n -C 3 F 7（4）；n -C 4 F 9（5）]和（TMEDA）PdI 2以及分别为1和2。用I 2处理1或2得到相应的碘化物4和5，消除了CH 3 I，而类似的反应是2用浓盐酸制得氯化物（TMEDA）PdCl（C 4 F 9）（8）。相反，（TMEDA）Pd（CH 3）2与仲碘化物ICF（CF 3）2反应仅得到一种氟代烷基产物，（TMEDA）Pd（CH
• Palladium(II) halide complexes of N,N,S-tridentate Schiff bases: synthesis, structural studies in solution and solid state, and analysis of Hirshfeld surfaces
  作者：Jesús-Alberto Alvarez-Hernández、Noemí Andrade-López、José G. Alvarado-Rodríguez、Oscar Muñoz-Granados、Gloria Sánchez-Cabrera、Diego Martínez-Otero

  DOI：10.1007/s11243-024-00580-z

  日期：——

  The synthesis and characterization of bromo- and iodo complexes of Pd(II) containing tridentate anionic Schiff bases, derived from the ring-opening of 2-R-2-(2-pyridyl)benzothiazoline precursors (R = H, 1; R = Me, 2; R = C6H5, 3; R = C5H4N, 4) is described. The [Pd(Ln)X] complexes [for X = Br: n = 1 (1a), n = 2 (2a), n = 3 (3a), and n = 4, (4a); for X = I: n = 1 (1b), n = 2 (2b), n = 3 (3b), and n = 4

  含有三齿阴离子席夫碱的 Pd(II) 溴代和碘代配合物的合成和表征，该配合物源自 2-R-2-(2-吡啶基)苯并噻唑啉前体的开环 (R = H, 1 ; R =描述了Me，2；R＝C 6 H 5，3；R＝C 5 H 4 N，4 )。 [Pd( L n ) X ] 配合物 [对于X  = Br：n  = 1 ( 1a )、n  = 2 ( 2a )、n  = 3 ( 3a ) 和n  = 4 ( 4a )；对于X  = I：n  = 1 ( 1b )、n  = 2 ( 2b )、n  = 3 ( 3b ) 和n  = 4 ( 4b )] 通过 NMR 和 IR 光谱以及元素分析在溶液和固态中进行表征分析。在所有配合物中，相应的阴离子席夫配体 L n } -显示κ 2 N κ S -三齿配位模式。 [Pd (L 3 )Br] ( 3a )、[Pd (L 3 )I] ( 3b )、[Pd (L
• Synthesis of Arylpalladium(II) Complexes Derived from Benzyl Alcohol, Reactivity toward Alkyl Halides, and Synthesis of Dinuclear Arylpalladium(II) Complexes
  作者：María-José Fernández-Rodríguez、Eloísa Martínez-Viviente、José Vicente、Peter G. Jones

  DOI：10.1021/acs.organomet.5b00309

  日期：2015.7.13

  The aryl palladium complexes [Pd-(C6H4CH2OH-2)(N<^>N)] (N<^>N = bpy = 2,2'-bipyridyl (1a), tbbpy 4,4'-di-tert-butyl-2,2'-bipyridine (1b), tmeda = N,N,N',N'-tetramethylethylenediamine (1c)) were synthesized by oxidative addition of 2-iodobenzyl alcohol to one equivalent of "[Pd(dba)2]" (dba = dibenzylideneacetone) in the presence of the N<^>N ligands. By reaction of la with three equivalents of XyNC (Xy = 2,6-dimethylphenyl) the insertion complex trans [PdIC(=NXy) (C6H4CH2OH-2)} (CNXy)(2)] (2) was formed. The reaction of 1a with (KOBu)-Bu-t resulted in the formation of the chelate complex [Pd(kappa(2)-C,O-C6H4CH2O-2)(bpy)] (3), which crystallizes as pairs of molecules bridged by hydrogen bonds to water of crystallization. Complex 3 reacts with XyNC, forming the cyclic imidate N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-imine (4). By various primary alkyl halides RCH2X, the complexes [PdX(C6H4CH2OCH2R-2)(bpy)] (X = I, R = H (5a), X = Br, R = Ph (5b), p-C6H4CH2Br (5c), p-C6H4Br (5d), and p-C6H4I (5e)) were obtained. When the reaction of 3 with p-C6H4(CH2Br)(2) was carried out in a 2:1 ratio, the dinuclear arylpalladium complex [(bpy)BrPd(C6H4CH2OCH2-2)}2(C6H4-1,4)] (6) formed. An halide exchange reaction on Se, using AgOTf and an excess of NaI, afforded [PdIC6H4(CH2OCH2(C6H4I-4))-2}(bpy)] (5f), which by oxidative addition to [Pd(dba)(2)] in the presence of bpy formed another dinuclear arylpalladium complex, Rbpy)IPd(C6H4CH2-2)O(CH2C6H4-4)PdI(bpy)] (7). All the complexes have been extensively characterized by NMR spectroscopy. The crystal structures of la, 3 center dot H2O, and Se were determined by X-ray diffraction studies.
• Synthesis and Reactivity of Ortho-Palladated Arylureas. Synthesis and Catalytic Activity of a C,N,C Pincer Complex. Stoichiometric Syntheses of Some N-Heterocycles
  作者：José Vicente、José-Antonio Abad、Joaquín López-Serrano、Peter G. Jones、Carmen Nájera、Luis Botella-Segura

  DOI：10.1021/om050451y

  日期：2005.10.1

  1-(2-lodophenyl)-3-p-tolylurea (1) reacts with Pd(dba)(2) ([Pd-2(dba)(3)]-dba; dba = dibenzylideneacetone) in the presence of the appropriate ligands to give the ortho-palladated arylureas [PdC6H4NHC(O)NHTo-2}IL2] (To = C6H4Me-4; L-2 = tbubpy (4,4'-di-tert-butyl-2,2'-bipyridine) (2a), tmeda (N,N,N ',N '-tetramethylethylenediamine) (2b); L = PPh3 (2c)). Reaction of 2b with Tl(TfO) TfO = triflate, CF3SO3) results in the formation of cyclopalladated [Pdkappa C-2,O- C6H4NHC(O)NHTo-2}(tmeda)]OTf (3b). The latter reacts with PPh3 to yield [PdC6H4NHC-(O)NHTo-2}(tmeda)(PPh3)]OTf (4b). Treatment of 2b with CO gives the corresponding acyl derivative [PdC(O)C6H4NHC(O)NHTo-2}I(tmeda)] (5b). If Tl(TfO) is added after the bubbling of CO, the C,N coupling product 3-p-tolyl-1H-quinazoline-2,4-dione (6) is formed. Complex 5b reacts with XyNC (Xy = 2,6-dimethylphenyl) to yield trans- [PdC(O)C6H4NHC-(O)NHTo-2}I(CNXy)(2)] (7). Both 5b and 7 decompose in solution to give 6. Complex 2b reacts with isocyanides to give the iminoacyl derivatives trans-[PdC(=NR)C6H4NHC(O)NHTo-2}I(CNR)2] (R = Xy (8x), Bu-t (8t)). The complex 8x gives the C,N coupling product 4-(xylylimino)-3-p-tolyl-3,4-dihydro-1H-quinazolin-2-one (9) after treatment with TlOTf 8x also reacts with bases (K2CO3 and Tl2CO3) to yield the iminoacyl amido carbene C,N,C pincer palladium complex [Pdkappa C-3,N,C-C(=NXy)C6H4NC(O)NToC(NHXy)-2}(CNXy)] (10); this complex is an active precatalyst in Heck and Suzuki reactions. The reaction of 2b with R'C equivalent to CR" and TIOTf gives [Pdkappa C-2,N-CR'=CR"C6H4NHC(O)NHTo-2}(tmeda)]OTf (R' = R" = Et (11be), CO2Me (11bm), Ph (11bp); R' = Ph, R" = CO2Me (11bq)). These complexes decompose in solution, and in the case of 11bp, 2,3-diphenylindole-l-carboxylic acid p-tolylamide (12p) was isolated. 11bq reacts with PPh3 to give 3-phenyl-1H-indole-2carboxylic acid methyl ester (13q). 11bp and 11bq decompose in the presence of CO to yield 3,4-diphenyl-2-quinolone (14po) and 2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qo), respectively. Similarly, when 11bq is reacted with XyNC, the C,N coupling compound 2-xylyl-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qnx) is formed. The crystal and molecular structures of 3b, 10-0.5CDCl(3), 11bp-OEt2, 11bq, and 14po have been determined.