[{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2] | 1289199-86-5

• 英文名称: [{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2]
• 英文别名: [{Rh(μ-Cl)(2-para-tolyl-pyridinato)₂}₂]；[{Rh(μ-Cl)(2-(p-tolyl)pyridinato)₂}₂]； [Rh(μ-Cl)( 2-(p-tolyl)pyridinato)]2；[{Rh(μ-Cl)(ptpy)₂}₂]；{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2；{Rh(μ-Cl)(para-tolyl-pyridinato)2}2；[Rh(μ-Cl)(2-(p-tolyl)pyridinato)2]2
• CAS: 1289199-86-5
• 化学式: C₄₈H₄₀Cl₂N₄Rh₂
• 分子量: 949.589
• InChiKey: FDDPCCMCSKSVFR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4,4'-二氨基-2,2'-联吡啶 、 [{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2] 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  含有 5-取代的 1,10-菲咯啉或 4,4'-取代的 2,2'-联吡啶配体的双环金属化 M(III) 配合物 (M=Rh, Ir) 的细胞毒活性

  摘要：

  八种新型双环金属化合物[ M (ptpy) 2 (N^N)]PF 6 (ptpy=2-( p -tolyl )pyridinato; N^N=5-chloro-1,10-phenanthroline )的合成与表征: M =Rh, 1 ; M=Ir, 2 ); N^N=5-甲基-1,10-菲咯啉：M =Rh, 3 ; M=Ir, 4 ; N^N=4,4'-二苯基-2,2'-联吡啶：M =Rh, 5 ; M = Ir, 6 ; N^N=4,4'-二氨基-2,2'-联吡啶：M =Rh, 7 ; M = Ir, 8) 进行了描述。所有化合物均通过光谱手段进行表征。此外，通过单晶X射线衍射研究确定了晶体中化合物4、5、6和8的分子结构。为了探索所有新八种化合物的细胞毒性特性，进行了针对主要癌细胞系 MCF-7 和 HT-29 的比色测定（MTT 测定）。确定的 IC 50值在 1.3-5.6 μM

  DOI：

  10.1002/zaac.202200206
• 作为产物：
  描述：

  2-(4-甲基苯基)吡啶 、 chlorobis(cyclooctene)-iridium(I) dimer 以 甲苯 为溶剂， 反应 1.0h， 生成 [{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2]
  参考文献：
  名称：

  Photophysical and biological characterization of new cationic cyclometalated M(III) complexes of rhodium and iridium

  摘要：

  Synthesis and characterization of new cyclometalated complex salts [M(ptpy)(2)(ddmp)]PF6 (M = Rh, 1; M = Ir, 2; ptpy = 2-(p-tolyl)pyridinato; ddmp = 4,7-dichloro-2,9-dimethyl-1,10-phenanthroline) is described. Compounds 1 and 2 were obtained by the reaction of ddmp with the complexes [(M(mu-Cl)(ptpy)(2)}(2)] (M = Rh, Ir) in a mixture of CH2Cl2/MeOH/H2O under reflux conditions. The compounds 1 and 2 crystallized from dichloromethane/chloroform/hexane in the triclinic space group P (1) over bar and their molecular structures were confirmed by single-crystal X-ray diffraction. Compound 2 exhibits strong yellow phosphorescence in a polymer matrix and in solution at ambient temperature. Both compounds display significant cytotoxicity against human cancer cell lines with the IC50 values in the high nano-molar range. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.04.031

文献信息

• Bis‐cyclometalated Rhodium and Iridium Chloride Complexes Yield Different Products Upon Reaction With 9,10‐Diaminophenanthrene
  作者：Marion Graf、Daniel Siegmund、Nils Metzler‐Nolte、Karlheinz Sünkel

  DOI：10.1002/zaac.201900147

  日期：2019.9.13

  The reaction of 9.10‐diaminophenanthrene with [Rh(μ‐Cl)(ptpy)2}2] yields – quite unexpected – the new cyclometalated complex salts [Rh(ptpy)2(9,10‐diiminophenanthrene)]PF6 (1), whereas with the corresponding dinuclear iridium compound the “usual” [Ir(ptpy)2(9,10‐diaminophenanthrene)]PF6 (2) is obtained. The molecular structure of compound 1 was confirmed by single‐crystal X‐ray diffraction. 1 crystallized

  9.10-二氨基菲与 [Rh(μ-Cl)(ptpy)2}2] 的反应产生了非常出人意料的新环金属化络盐 [Rh(ptpy)2(9,10-二亚氨基菲)]PF6 (1) ，而使用相应的双核铱化合物，则获得了“通常的”[Ir(ptpy)2(9,10-二氨基菲)]PF6 (2)。化合物1的分子结构由单晶X射线衍射证实。1 在单斜空间群 P21/n 中结晶为二氯甲烷溶剂化物。两种化合物对人癌细胞系均显示出显着的细胞毒性，IC50 值在低微摩尔范围内。
• A small molecule HIF-1α stabilizer that accelerates diabetic wound healing
  作者：Guodong Li、Chung-Nga Ko、Dan Li、Chao Yang、Wanhe Wang、Guan-Jun Yang、Carmelo Di Primo、Vincent Kam Wai Wong、Yaozu Xiang、Ligen Lin、Dik-Lung Ma、Chung-Hang Leung

  DOI：10.1038/s41467-021-23448-7

  日期：——

  Impaired wound healing and ulcer complications are a leading cause of death in diabetic patients. In this study, we report the design and synthesis of a cyclometalated iridium(III) metal complex 1a as a stabilizer of hypoxia-inducible factor-1α (HIF-1α). In vitro biophysical and cellular analyses demonstrate that this compound binds to Von Hippel-Lindau (VHL) and inhibits the VHL–HIF-1α interaction. Furthermore, the compound accumulates HIF-1α levels in cellulo and activates HIF-1α mediated gene expression, including VEGF, GLUT1, and EPO. In in vivo mouse models, the compound significantly accelerates wound closure in both normal and diabetic mice, with a greater effect being observed in the diabetic group. We also demonstrate that HIF-1α driven genes related to wound healing (i.e. HSP-90, VEGFR-1, SDF-1, SCF, and Tie-2) are increased in the wound tissue of 1a-treated diabetic mice (including, db/db, HFD/STZ and STZ models). Our study demonstrates a small molecule stabilizer of HIF-1α as a promising therapeutic agent for wound healing, and, more importantly, validates the feasibility of treating diabetic wounds by blocking the VHL and HIF-1α interaction.

  摘要：受损伤口愈合和溃疡并发症是糖尿病患者死亡的主要原因。在这项研究中，我们报道了一种环金属化的铱（III）金属配合物1a的设计和合成，作为缺氧诱导因子-1α（HIF-1α）的稳定剂。体外生物物理和细胞分析表明，该化合物结合Von Hippel-Lindau（VHL）并抑制VHL-HIF-1α相互作用。此外，该化合物在细胞内累积HIF-1α水平，并激活HIF-1α介导的基因表达，包括VEGF、GLUT1和EPO。在活体小鼠模型中，该化合物显著加快了正常和糖尿病小鼠的伤口闭合速度，糖尿病组效果更显著。我们还证明了与伤口愈合相关的HIF-1α驱动基因（如HSP-90、VEGFR-1、SDF-1、SCF和Tie-2）在1a处理的糖尿病小鼠（包括db/db、HFD/STZ和STZ模型）的伤口组织中增加。我们的研究证明了一种小分子稳定剂HIF-1α作为治疗伤口愈合的有前途的药物，并更重要的是，通过阻断VHL和HIF-1α相互作用验证了治疗糖尿病伤口的可行性。
• Towards the new cyclometalated complex [{Rh(μ-Cl)(ptpy)2}2] (ptpy = 2-(p-tolyl)pyridinato)
  作者：Karlheinz Sünkel、Marion Graf、Hans-Christian Böttcher、Beatrice Salert、Hartmut Krüger

  DOI：10.1016/j.inoche.2011.01.018

  日期：2011.4

  convenient synthesis of the cyclometalated complex [Rh(μ-Cl)(ptpy)2}2] (2, ptpy = 2-(p-tolyl)pyridinato) is described. Compound 2 was obtained by oxidative addition of Hptpy towards [Rh(μ-Cl)(coe)2}2] 1 (coe = cis-cyclooctene) in refluxing toluene in good yield. The complex 2 crystallized from chloroform/iso-hexane in the space group P21/n as solvate 2*2 CHCl3 and its molecular structure was confirmed

  摘要 描述了环金属化配合物 [Rh(μ-Cl)(ptpy)2}2] (2, ptpy = 2-(p-tolyl)pyridinato) 的方便合成。通过在回流甲苯中将Hptpy氧化加成到[Rh(μ-Cl)(coe)2}2] 1 (coe = cis-cyclooctene)，以良好的收率获得化合物2。复合物 2 在空间群 P21/n 中从氯仿/异己烷中结晶为溶剂化物 2*2 CHCl3，其分子结构由单晶 X 射线衍射研究证实。发射光谱显示新化合物为发绿光的磷光复合物。
• Synthesis, characterization and studies on the biological activity of bis-cyclometalated M(III)-complexes (M = Rh, Ir and Ru)
  作者：Marion Graf、Daniel Siegmund、Nils Metzler-Nolte、Karlheinz Sünkel、Hans-Christian Böttcher

  DOI：10.1016/j.ica.2018.11.050

  日期：2019.3

  Abstract The synthesis and characterization of new cyclometalated complex salts [M(ptpy)2(4,4-HOCH2bpy)]PF6 (M = Rh, 1; M = Ir, 2 and M = Ru, 4; ptpy = 2-(p-tolyl)pyridinato; 4,4-HOCH2bpy = 4,4-bis(hydroxymethyl)-2,2-bipyridine) is reported. Compounds 1 and 2 were obtained by bridge-splitting reaction of complexes [M(µ-Cl)(ptpy)2}2] (M = Rh, Ir) with the ligand 4,4-HOCH2bpy in refluxing CH2Cl2/MeOH/H2O

  摘要新型环金属盐[M（ptpy）2（4,4-HOCH2bpy）] PF6（M = Rh，1; M = Ir，2 and M = Ru，4; ptpy = 2-（p -甲苯基）吡啶基；报道了4，4-HOCH2bpy ＝ 4，4-双（羟甲基）-2，2-联吡啶。化合物1和2是通过将配合物[M（µ-Cl）（ptpy）2} 2]（M = Rh，Ir）与配体4,4-HOCH2bpy在回流CH2Cl2 / MeOH / H2O中进行桥拆分反应而获得的混合物。从前体化合物[Ru（μ-Cl）Cl（η6-C6H6）} 2]开始，通过多步合成获得化合物4。所有化合物均进行了全面表征（必要时进行元素分析，MS，IR，UV-Vis以及1H和13C NMR），并通过X射线衍射确认了化合物1和4的分子结构。所有新化合物均以低微摩尔范围的IC50值显示出对人癌细胞的显着细胞毒性。令人惊讶的是，中心金属似乎对生物活性没有重大影响。
• Metal and Substituent Influence on the Cytostatic Activity of Cationic Bis‐cyclometallated Iridium and Rhodium Complexes with Substituted 1,10‐Phenanthrolines as Ancillary Ligands
  作者：Marion Graf、Daniel Siegmund、Yvonne Gothe、Nils Metzler‐Nolte、Karlheinz Sünkel

  DOI：10.1002/zaac.201900317

  日期：2020.7.15

  Synthesis and characterization of the new cyclometalated complex salts [Rh(ptpy)2(5.6‐dimethyl‐1,10‐phenanthroline)]PF6 (1a) [Rh(ptpy)2(2.9‐dimethyl‐4.7‐diphenyl‐1,10‐ phenanthroline)]PF6 (2a), [Rh(ptpy)2(5‐amino‐1,10‐phenanthroline)] PF6 (3a), and [M(ptpy)2 (pyrazino‐[2.3‐f]‐1,10‐phenanthroline)]PF6 (M = Rh, 4a; M = Ir, 4b), (ptpy = 2‐(p‐tolyl)pyridinato) are described. The molecular structures of

  新型环金属化络盐[Rh(ptpy)2(5.6-二甲基-1,10-菲咯啉)]PF6(1a)[Rh(ptpy)2(2.9-二甲基-4.7-二苯基-1,10-)的合成与表征菲咯啉)]PF6 (2a), [Rh(ptpy)2(5-amino-1,10-phenanthroline)] PF6 (3a), 和 [M(ptpy)2 (pyrazino-[2.3-f]-1,10 -菲咯啉)]PF6 (M = Rh, 4a; M = Ir, 4b), (ptpy = 2-(p-tolyl)pyridinato)。通过单晶X射线衍射确定固态化合物1b和4a的分子结构。所有这些化合物及其已知的铱对应物 1b - 3b 对人癌细胞系 MCF-7（人乳腺癌）和 HT-29（结肠腺癌）显示出显着的细胞毒性，IC50 值在低微摩尔范围内。