sym N,N',N''-tris(2,5-xylyl)guanidine

• 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: sym N,N',N''-tris(2,5-xylyl)guanidine
• 英文别名: N,N’,N"-tri(2-tolyl)guanidine；1,2,3-Tris(2,5-dimethylphenyl)guanidine；1,2,3-tris(2,5-dimethylphenyl)guanidine
• 化学式: C₂₅H₂₉N₃
• 分子量: 371.525
• InChiKey: XSDSOKVDACJOMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  36.4
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  sym N,N',N''-tris(2,5-xylyl)guanidine 在 potassium carbonate 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 44.0h， 生成
  参考文献：
  名称：

  带有乙酰丙酮和吡啶甲酸辅助配体的杂配环铂胍(1−)配合物的合成、结构、光物理和理论研究

  摘要：

  对称N , N ', N ''-三芳基胍 (ArNH) 2 C 的环铂化 NAr 与cis -[Pt(TFA) 2 (S(O)Me 2 ) 2 ] 在甲苯中得到cis -[Pt(TAG)(TFA)(S(O)Me 2 )] (TAG = 三芳基胍(1−) -κ C ,κ N ; TFA = OC(O)CF 3 ; 6–9 ) 产率 75–82%。 6–9和先前已知的顺式 -[Pt(TAG)X(S(O)Me 2 )] (X = Cl ( 1 ) 和 TFA ( 2–5 )) 与乙酰丙酮 (acacH) 或 2- 的反应吡啶甲酸 (picH) 在碱存在下提供 [Pt(TAG)(acac)] (acac = 乙酰丙酮酸-κ 2 O , O ′; 10–18 ) 和 [Pt(TAG)(pic)] (pic = 2-吡啶甲酸-κ N ,κ O ; 19 ) 产量高。通过分析、红外和多核核磁共振光谱对新

  DOI：

  10.1039/d4ra00828f
• 作为产物：
  描述：

  2,5-二甲基苯胺 在 potassium hydroxide 作用下， 以 乙醇 、 水 、 硝基苯 为溶剂， 生成 sym N,N',N''-tris(2,5-xylyl)guanidine
  参考文献：
  名称：

  Dual Role of Acetate as a Nucleophile and as an Internal Base in Cycloplatination Reaction of sym-N,N′,N″-Triarylguanidines

  摘要：

  Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of sym-N,N',N ''-triarylguanidines, ArN=C(NHAr)(2) (sym = symmetrical; Ar = 2-MeC6H4 (LH22-tolyl), 2-(MeO)C6H4 (LH22-anisyl), 4-MeC6H4 (LH24-tolyl), 2,5-Me2C6H3 (LH22,5-xylyl), and 2,6-Me2C6H3 (LH22,6-xylyl)) in toluene under reflux condition for 3 h afforded cis- or trans-[Cl2Pt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (1), 2-(MeO)C6H4 (2), 4-MeC6H4 (3), 2,5-h Me2C6H3 (4), and 2,6-Me2C6H3 (5), respectively) in 83-96% yield. Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-tolyl and LH24-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 h afforded acetate-substituted products, cis-[(AcO)ClPt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (6) and 4-MeC6H4 (7)) in 83% and 84% yields, respectively. Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-anisyl and LH22-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 and 12 h afforded six-membered [C,N] platinacycles, [Pt{kappa(2)(C,N)-C6H3R-3(NHC(NHAr)(=NAr))-2}Cl(S(O)Me-2)] (Ar = 2-RC6H4; R = OMe (8) and Me (9)), in 92% and 79% yields, respectively. The new complexes have been characterized by analytical and spectroscopic techniques, and further the molecular structures of 1, 2, 4, 5, 6, and 8 have been determined by single-crystal X-ray diffraction. The platinum atom in 1, 4, and 5 exhibited the trans configuration, while that in 2, 6, and 8 exhibited the cis configuration. Complex 6 is shown to be the precursor for 9, and the former is suggested to transform to the latter possibly via an intramolecular C-H activation followed by elimination of AcOH. The solution behavior of new complexes has been studied by multinuclear NMR (H-1, Pt-195, and C-13) spectroscopy. The new complexes exist exclusively as a single isomer (trans (1 and 5) and cis (6 and 7)), a mixture of cis and trans isomers with the former isomer being predominant in the case of 2 and the latter isomer being predominant in the case of 3. Complex 5 in the trans form revealed the presence of one isomer at 0.007 mM concentration and two isomers in about 1.00:0.12 ratio at 0.154 mM concentration as revealed by H-1 NMR spectroscopy, and this has been ascribed to the restricted Pt-S bond rotation at higher concentration. Platinacycle 8 exists as one isomer, while 9 exists as a mixture of seven isomers in solution. The influence of steric factor, pi-acceptor property of the guanidine, subtle solid-state packing forces upon the configuration of the platinum atom, and the number of isomers in solution have been outlined. Factors that accelerate or slow down the cycloplatination reaction, the role of NaOAc, and a plausible mechanism of this reaction have been discussed.

  DOI：

  10.1021/ic302058u

文献信息

• Syntheses, characterization, solution behavior and catalytic activity of trans-[(guanidine)2PdX2] (X = Cl and OC(O)R; R = Me, Ph and Bu) in Heck–Mizoroki coupling reactions involving chloroarenes/methyl acrylate
  作者：Palani Elumalai、Rishabh Ujjval、Munirathinam Nethaji、Natesan Thirupathi

  DOI：10.1016/j.poly.2018.05.022

  日期：2018.9

  2·CHCl3, 3·C7H8 and 4 contain a pair of R11(8) rings stabilized by an intramolecular N–H⋯O hydrogen bond between the guanidine ligand and the carboxylate moiety. The influence of shape and size of the anion upon the stereochemistry of the complexes in the solid state and in solution are discussed. VT 1H NMR spectroscopic studies carried out on samples of 1 and 3 revealed the presence of a mixture of two

  摘要反式[（（ArNH）2C NAr} 2PdX2]（Ar = 2,5-Me2C6H3; X = Cl（1）和OC（O）R; R = Me（2），Ph（3）和tBu（ 4））以高收率分离，并通过元素分析，IR和NMR（1H和13C）光谱进行了表征。上述配合物的分子结构通过单晶X射线衍射测定，揭示了反式反抗-反式（1·CHCl3），反式反抗-syn（2·CHCl3和3·C7H8）和反式反抗-（1·CHCl3）。 4）固态立体化学。配合物2·CHCl3、3·C7H8和4含有一对R11（8）环，该环通过胍配体和羧酸酯部分之间的分子内N–H = O氢键稳定。讨论了阴离子的形状和大小对固态和溶液中配合物的立体化学的影响。对1和3样品进行的VT 1H NMR光谱研究表明，溶液中存在两种旋转异构体的混合物，这是由于两种配体中胍配体的CN（H）Ar单键旋转受限制而产生的。配合物1-4被证明是活性催化剂，
• Influence of the Steric/Electronic Properties of <i>N</i>-Aryl Substituents in Cycloplatinated Guanidinate(1−) Complexes on the Formation of Discrete Pt → Ag Complexes and One-Dimensional Coordination Polymer
  作者：Nitish Kumar Sinha、Vishwesh Mishra、Natesan Thirupathi

  DOI：10.1021/acs.inorgchem.2c04172

  日期：2023.5.22

  The reactions of cycloplatinated guanidinate(1−) complexes 1–6 with AgTFA (TFA = OC(O)CF3) in 1:1 and 1:2 PtII/AgI molar ratios afforded complexes containing three types of Pt2Ag2 skeletons (7–10, 11, and 13), one 1D CP containing Pt2Ag3 skeleton (16), and a Pt2Ag4 complex (17) in 91–95% (method 1), 73–82% (method 2) (7–10), and 54–79% (11, 13, 16, and 17) yields. The reactions of 11 with 2,6-XylNC

  环铂胍 (1−) 配合物1 – 6与 AgTFA (TFA = OC(O)CF 3 ) 以 1:1 和 1:2 Pt II /Ag I摩尔比反应得到含有三种 Pt 2 Ag 2的配合物骨架（7 – 10、11和13 ）、一个包含 Pt 2 Ag 3骨架的一维 CP ( 16 ) 和一个 Pt 2 Ag 4复合物 ( 17 )，浓度为 91–95%（方法 1）、73–82%（方法 2) ( 7 – 10 ), 和 54–79% (11、13、16和17 )产量。_ _ 11与 2,6-XylNC（2,6-Xyl = 2,6-Me 2 C 6 H 3）和 4-DMAP（4-二甲氨基吡啶）反应得到中性络合物18和离子络合物19， 分别。通过单晶 X 射线衍射明确确定了 12 种配合物的分子结构。十个复合物包含前所未有的 PtAg 骨架，并显示包含多个由 TFA 配体支持的配位 Pt → Ag 键，TAG
• Dual Role of Acetate as a Nucleophile and as an Internal Base in Cycloplatination Reaction of <i>sym</i>-<i>N</i>,<i>N</i>′,<i>N</i>″-Triarylguanidines
  作者：Palani Elumalai、Natesan Thirupathi、Munirathinam Nethaji

  DOI：10.1021/ic302058u

  日期：2013.2.18

  Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of sym-N,N',N ''-triarylguanidines, ArN=C(NHAr)(2) (sym = symmetrical; Ar = 2-MeC6H4 (LH22-tolyl), 2-(MeO)C6H4 (LH22-anisyl), 4-MeC6H4 (LH24-tolyl), 2,5-Me2C6H3 (LH22,5-xylyl), and 2,6-Me2C6H3 (LH22,6-xylyl)) in toluene under reflux condition for 3 h afforded cis- or trans-[Cl2Pt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (1), 2-(MeO)C6H4 (2), 4-MeC6H4 (3), 2,5-h Me2C6H3 (4), and 2,6-Me2C6H3 (5), respectively) in 83-96% yield. Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-tolyl and LH24-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 h afforded acetate-substituted products, cis-[(AcO)ClPt(S(O)Me-2)(ArN=C(NHAr)(2))] (Ar = 2-MeC6H4 (6) and 4-MeC6H4 (7)) in 83% and 84% yields, respectively. Reaction of cis-[Cl2Pt(S(O)Me-2)(2)] with 1 equiv of LH22-anisyl and LH22-tolyl in the presence of 1 equiv of NaOAc in methanol under reflux condition for 3 and 12 h afforded six-membered [C,N] platinacycles, [Ptkappa(2)(C,N)-C6H3R-3(NHC(NHAr)(=NAr))-2}Cl(S(O)Me-2)] (Ar = 2-RC6H4; R = OMe (8) and Me (9)), in 92% and 79% yields, respectively. The new complexes have been characterized by analytical and spectroscopic techniques, and further the molecular structures of 1, 2, 4, 5, 6, and 8 have been determined by single-crystal X-ray diffraction. The platinum atom in 1, 4, and 5 exhibited the trans configuration, while that in 2, 6, and 8 exhibited the cis configuration. Complex 6 is shown to be the precursor for 9, and the former is suggested to transform to the latter possibly via an intramolecular C-H activation followed by elimination of AcOH. The solution behavior of new complexes has been studied by multinuclear NMR (H-1, Pt-195, and C-13) spectroscopy. The new complexes exist exclusively as a single isomer (trans (1 and 5) and cis (6 and 7)), a mixture of cis and trans isomers with the former isomer being predominant in the case of 2 and the latter isomer being predominant in the case of 3. Complex 5 in the trans form revealed the presence of one isomer at 0.007 mM concentration and two isomers in about 1.00:0.12 ratio at 0.154 mM concentration as revealed by H-1 NMR spectroscopy, and this has been ascribed to the restricted Pt-S bond rotation at higher concentration. Platinacycle 8 exists as one isomer, while 9 exists as a mixture of seven isomers in solution. The influence of steric factor, pi-acceptor property of the guanidine, subtle solid-state packing forces upon the configuration of the platinum atom, and the number of isomers in solution have been outlined. Factors that accelerate or slow down the cycloplatination reaction, the role of NaOAc, and a plausible mechanism of this reaction have been discussed.
• Syntheses, structural, photophysical and theoretical studies of heteroleptic cycloplatinated guanidinate(1−) complexes bearing acetylacetonate and picolinate ancillary ligands
  作者：Vasudha Thakur、Jisha Mary Thomas、Mohammad Adnan、Chinnappan Sivasankar、G. Vijaya Prakash、Natesan Thirupathi

  DOI：10.1039/d4ra00828f

  日期：2024.4.22

  determined by single crystal X-ray diffraction. Absorption spectra of 10–19 in solution and their emission spectra in crystalline form were measured. Platinacycles 10–19 are bluish green light emitter in the crystalline form, and emit in the λPL = 488–529 nm range (11 and 13–19) while 12 emits at λPL = 570 nm. Unlike other platinacycles, the emission band of 12 is broad, red shifted, and this pattern is

  对称N , N ', N ''-三芳基胍 (ArNH) 2 C 的环铂化 NAr 与cis -[Pt(TFA) 2 (S(O)Me 2 ) 2 ] 在甲苯中得到cis -[Pt(TAG)(TFA)(S(O)Me 2 )] (TAG = 三芳基胍(1−) -κ C ,κ N ; TFA = OC(O)CF 3 ; 6–9 ) 产率 75–82%。 6–9和先前已知的顺式 -[Pt(TAG)X(S(O)Me 2 )] (X = Cl ( 1 ) 和 TFA ( 2–5 )) 与乙酰丙酮 (acacH) 或 2- 的反应吡啶甲酸 (picH) 在碱存在下提供 [Pt(TAG)(acac)] (acac = 乙酰丙酮酸-κ 2 O , O ′; 10–18 ) 和 [Pt(TAG)(pic)] (pic = 2-吡啶甲酸-κ N ,κ O ; 19 ) 产量高。通过分析、红外和多核核磁共振光谱对新