trans-[Pd(C(=NC6H3Me2-2,6)C6H4NH2-2)I(CNC6H3Me2-2,6)2] | 399566-92-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-[Pd(C(=NC6H3Me2-2,6)C6H4NH2-2)I(CNC6H3Me2-2,6)2]
• 英文别名: trans-[PdI(C(N(xylyl))C6H4NH2-2)(CN(xylyl))2]；trans-[PdI(CNC6H3Me2-2,6)2(C(NC6H3Me2-2,6)C6H4NH2-2)]；trans-[PdI(C(=NXy)NH2C6H4-2)(CNC6H3(CH3)2)2]；2-[(2,6-dimethylphenyl)iminomethyl]aniline;2-isocyano-1,3-dimethylbenzene;palladium(2+);iodide
• CAS: 399566-92-8
• 化学式: C₃₃H₃₃IN₄Pd
• 分子量: 718.976
• InChiKey: ISPLSVGVTKNFPR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.22
• 重原子数：
  39
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  47.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  trans-[Pd(C(=NC6H3Me2-2,6)C6H4NH2-2)I(CNC6H3Me2-2,6)2] 以 二氯甲烷 为溶剂， 生成 [PdI(CN(xylyl))(PPh3)(C(NH(xylyl))C6H4NH2-2)](OTf)
  参考文献：
  名称：

  通过环化反应合成1,2-二氢喹唑啉-4-基钯配合物

  摘要：

  的反应的反式- [{器Pd1 C（═NXy）C 6 H ^ 4 NH 2 -2}（CNXy）2 ]（1，XY = C 6 H ^ 3我2 -2,6）与HO 3 SCF 3（HOTf ）和RC（O）R'提供反式[PdI {C═N（Xy）C（R）（R'）NHC 6 H 4 -2}（ CNXy）2 ] OTf（R = Me，R'= Me（2a），Ph（2b），CH 2 C（O）Me（2c），H（2d），R = H，R'= H（2e） ，CH═CH2（2f），Ph（2g），C 6 H 4 Me-4（To）（2h），{Fe（C 5 H 4）（C 5 H 5）}（Fc）（2i））。在不存在羰基化合物的情况下，1与HOTf的反应生成复杂的SP-4-4- [PdI { C，N -C（= NHXy）C 6 H 4 NH 2 -2} CNXy] OTf（3），可以与PPh 3反应，得到SP-4-3- [ PdI

  DOI：

  10.1021/om900616v
• 作为产物：
  描述：

  2,6-二甲基苯基异腈 以 二氯甲烷 、 甲苯 为溶剂， 生成 trans-[Pd(C(=NC6H3Me2-2,6)C6H4NH2-2)I(CNC6H3Me2-2,6)2]
  参考文献：
  名称：

  Synthesis and Reactivity toward Isonitriles of (2-Aminoaryl)palladium(II) Complexes

  摘要：

  Mixtures of "Pd(dba)(2)" (dba = dibenzylideneacetone) and 2,2'-bipyridine (bpy; 1:2) or N,N,N',N'-tetramethylethylenediamine (tmeda; 1:1) react with 2-bromo-4-nitroaniline to give [Pd{C6H3NH2-2-NO2-5}Br(N-N)] (N-N = bpy (1b), tmeda (1b')). Reactions of 2-iodoaniline with mixtures of "Pd(dba)(2)" and isonitriles RNC (R = C6H3Me2-2,6 (Xy), 2:1:2 molar ratios; R = Bu-t, 2.9:1:2 molar ratios) result in the formation of the complexes [Pd{kappa(2)C,N-C(=NXy)C6H4NH2-2}I(CNXy)] (2a) and trans- [Pd{C(=(NBu)-Bu-t)C6H4NH2-2}I((CNBu)-Bu-t)(2)] (3a*). The reactions of [Pd{C6H4NH2-2}I(bpy)] and 1b' with RNC give the complexes trans-[Pd{C(=NR)C6H3NH2-2-Y-5}}X(CNR)(2)] (Y = H, X = I, R = Xy (3a), Bu-t (3a*); Y = NO2, X = Br, R = Xy (3b), Bu-t (3b*)). Complexes 3 react with Tl(TfO) (TfO = CF3SO3) to give decomposition products, with the exception of 3a, which gives the cyclopalladated complex cis-[Pd{kappa(2)C,N-C(=NXy)C6H4NH2-2}(CNXy)(2)]Tfn (4a), Complex 2a or 3 reacts with Tl(TfO) in the presence of the corresponding ligand, L or L-2, to give the cationic complex [Pd{C(=NR)C6H3NH2-2-Y-5}(CNR)L-2]TfO (L = (BuNC)-Bu-t, Y = H (5a*), NO2 (5b*); L-2 = bpy, Y = H, R = Xy (6a), Bu-t (6a*)). When L = PPh3, the resulting complexes trans- [Pd{C(=NR)C6H3NH2-2-Y-5}(CN-Bu-t)(2)(PPh3)]TfO (Y = H (7a*), NO2 (7b*)) decompose easily to the Pd(I) complex [Pd-2(CN-Bu-t)(4)(PPh3)(2)](TfO)(2) (8). The reaction of 2a with Tl(TfO) affords [{Pd[kappa-(C),N-C(=NXy)C6H4NH2](CNXy)}(2)(mu-I)]TfO (9a), and that with a mixture of bpy and Tl(TfO) in acetone with subsequent bubbling of CO through the solution gives [Pd(R)(CNXy)(bpy)](TfO)(2) (10), where R is 2-(xylylamino)-3-xylylquinazolinium-4-yl. The crystal structures of 2a, 3a, 4a, 6a, 8, 9a.CH2Cl2, and 10.1.5CH(2)Cl(2) have been determined by X-ray diffraction studies. Some hydrogen bond interactions (C-sp(3)-H...Pd, N-H...pi-arene, N-H...I-Pd; eight-membered rings ...O-S-O...H-N-C-C-H... and ...I-Pd-N-H...I-Pd-N-H...) lead to interesting supramolecular structures.

  DOI：

  10.1021/om0104971

文献信息

• Mono-, Di-, and Trinuclear Palladium(II) Complexes Containing a Ligand with One, Two, or Three 1,2-Dihydroquinazolinium-4-yl Groups
  作者：José Vicente、María Teresa Chicote、Antonio J. Martínez-Martínez、Delia Bautista

  DOI：10.1021/om200188r

  日期：2011.4.25

  Complexes containing one, two, or three 1,2-dihydro-3-xylylquinazolinium-4-yl palladium units are obtained by reacting dialdehydes (C6H4(CHO)2-1,4, C6H4(CHO)2-1,3, 1,1′-ferrocenedicarboxaldehyde) or the trialdehyde 1,3,5-tris-(4-formylphenyl)benzene) with 1, 2, or 3 equiv of each of the amino(iminobenzoyl) complex trans-[PdIC(═NXy)C6H4NH2-2}(CNXy)2] (Xy = C6H3Me2-2,6) and triflic acid (HOTf), through

  通过使二醛（C 6 H 4（CHO）2 -1,4，C 6 H 4（CHO）2）反应获得包含一个，两个或三个1,2-二氢-3-二甲苯基喹唑啉-4-基钯单元的配合物-1,3-，1,1'- ferrocenedicarboxaldehyde）或三醛1,3,5-三- （4-甲酰基苯基）苯）用1，2，或每个氨基（iminobenzoyl的3当量）络合物的反式- [ PdI C（═NXy）C 6 H 4 NH 2 -2}（CNXy）2 ]（Xy = C 6 H 3 Me 2-2,6）和三氟甲磺酸（HOTf），通过在醛和2-氨基之间形成的亚胺加氢亚胺化来实现。确定了由C 6 H 4（CHO）2 -1,4和C 6 H 4（CHO）2 -1,3制备的双核衍生物的晶体结构，并研究了双核二茂铁基衍生物的电化学行为。
• Synthesis and Reactivity of [PdCl₂{<i>C,N</i>-C₆H₄C(═NHXy)NH₂-2}] and Neutral Palladium 1,2-Dihydroquinazolinium-4-yl Complexes: Depalladation Reactions
  作者：Antonio-Jesús Martı́nez-Martínez、José Vicente、Marı́a-Teresa Chicote、Delia Bautista

  DOI：10.1021/om200986k

  日期：2012.4.9

  The complex [PdC,N,O-C(=NXy)C6H4NC(Me)CHC(Me)O}-2}PPh3] (A) reacts with aqueous HCl and H2O2 or with aqueous HCl (HCl:Pd = 2, 3) to produce the complexes [PdCl2C,N-C(=NHXy)C6H4NH2-2}] (1), cis-[PdCl2C(= NHXy)C6H4NH2-2}}(PPh3)] (2c), and [PdCl2C(=NHXy)C6H4NH3-2}PPh3]Cl (3), respectively. The reactions of complex 1 with L (neutral C- or P-donor ligands) give [PdCl2C(=NHXy)C6H4NH2}-2}L] (2). Dehydrochlorination of 2a (L = (CNBu)-Bu-t) occurred upon heating to give [PdClC,N-C(=NXy)C6H4NH2-2}L] (4). The complexes [PdClC,N-C(=NXy)C6H4NH2-2}PPh3]X (X = ClO4 (5), TfO (5')) were obtained by reacting 2c with AgClO4 or TlTfO (TfO = CF3SO3), respectively. When 1 was reacted with NEt3, a dehydrochlorination/dimerization process occurred, giving [Pd2Cl2mu-N,C,N'-C(=NXy)C6H4NH2-2}(2)] (6a), which, in turn, reacted in two steps with TITfO and NaOAc to give [Pd-2(OAc)(2)mu-N,C,N'-C(=NXy)C6H4NH2-2}(2)] (6b). The reaction of 1 with 1 equiv of a neutral ligand L and a carbonyl compound (acetone, RCHO, or R'(CHO)(3)) affords the neutral 1,2-dihydroquinazolinium-4-yl complexes cis[PdCl2C(=NXy)CMe2NHC6H4-2}L] (7), cis-[PdCl2C(=NXy)CH(R)NHC6H4-2}PPh3) (8), and [cis-PdCl2C(=NXy)CHNHC6H4-2}CNXy}(3)mu(3)-C6H3(C6H4-4)(3)-1,3,5}] (9)), respectively. Depalladation of compounds 7 occurred when they were heated with TITfO, to give 2-Me-4-xylyliminium-1,4-dihydroquinoline triflate (10a). The complexes trans-[PdIC(=NXy)CMe2NHC6H4-2}(CNXy)(2)]TfO and trans-[PdIC(=NXy)C6H4NH2-2}(CNXy)(2)] react in two steps with AgTfO and PhC CH/NEt3 to give the depalladated species 2,2-dimethyl-3-xylyl-4-phenylethynyl-1,2-dihydroquinazolinium triflate (11) and H2NC6H4C(=NXy)C CPh}-2 (12), respectively. Complex 11 reacts with (KBuO)-Bu-t or Tl(acac) to give the dinuclear complex [Pd-2mu-C,N-C(=NXy)C6H4NH-2}C,N-C(=NXy)C6H4NH2-2}(CNXy)(3)] (13).