(meso-tetraphenylporphyrinato)-chloro-pyridyl-chromium | 65013-13-0

• 英文名称: (meso-tetraphenylporphyrinato)-chloro-pyridyl-chromium
• 英文别名: chloro(5,10,15,20-tetraphenylporphinato)chromium(III)(pyridine)；[Cr(5,10,15,20-tetraphenylporphinate)Cl(pyridine)]；ClCr(III)TPP-Py；[Cr(TPP)(Cl)(Py)]；(pyridine)chloro(5,10,15,20-tetraphenylporphyrinato)chromium(III)
• CAS: 65013-13-0
• 化学式: C₄₉H₃₃ClCrN₅
• 分子量: 779.284
• InChiKey: MIQLUMNWYCANQO-NBICUONBSA-M

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：

  (meso-tetraphenylporphyrinato)-chloro-pyridyl-chromium 在 丙酮 作用下， 以 neat (no solvent) 为溶剂， 生成 ClCr(III)TPP-Ac
  参考文献：
  名称：

  氯铬鎓（III）四苯基卟啉一元吡啶化物在丙酮中的光解离。激光光解反应态与配体交换反应的研究

  摘要：

  丙酮中的标题化合物ClCr（III）TPP-Py（Py =吡啶）光解离了轴向吡啶，可能是从4 S 1状态开始的，得到的ClCr（III）TPP为初始产物，在532上产率为≈0.16和355 nm激发。初始产物ClCr（III）TPP与吡啶和丙酮反应生成ClCr（III）TPP-Py和ClCr（III）TPP-Ac（Ac =丙酮）。单丙酮酸酯络合物ClCr（III）TPP-Ac进一步将轴向丙酮换成吡啶，以再生ClCr（III）TPP-Py。

  DOI：

  10.1016/0009-2614(90)87194-v
• 作为产物：
  描述：

  Cr(II)(meso-tetraphenylporphyrinato) 在 氧气 作用下， 以 二氯甲烷 为溶剂， 生成 (meso-tetraphenylporphyrinato)-chloro-pyridyl-chromium
  参考文献：
  名称：

  Dual Application of (Aqua)(Chlorido)(Porphyrinato)Chromium(III) as Hypersensitive Amine-Triggered ON Switch and for Dioxygen Activation

  摘要：

  Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr-III(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr-III(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O-2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O-2 as initial oxidant.

  DOI：

  10.1021/ic501644z

文献信息

• Laser Photolysis of Chromium(III) Porphyrins with Axial Pyridines in Dichloromethane and Toluene Solutions. Novel Effects of a Hydrogen Bond in the Ligand Exchange Reaction
  作者：Masahiko Inamo、Hideyuki Nakaba、Kiyohiko Nakajima、Mikio Hoshino

  DOI：10.1021/ic0002059

  日期：2000.10.1

  H2O to give [Cr(TPP)(Cl)(H2O)], which eventually exchanges the axial H2O with Py to regenerate [Cr(TPP)(Cl)(Py)]. The rate for the ligand exchange of [Cr(TPP)(Cl)(H2O)] with exogenous Py is found to exhibit a bell-shaped pyridine-concentration dependence. Kinetic studies revealed that at a high Py concentration, the exogenous Py probably makes a hydrogen bond with the axial H2O of [Cr(TPP)(Cl)(H2O)] to

  在含有二氯甲烷和甲苯的水中对 (氯)(吡啶)(5,10,15,20-四苯基卟啉)铬 (III), [Cr(TPP)(Cl)(Py)] 进行了激光光解研究。吡啶从 [Cr(TPP)(Cl)(Py)] 光诱导解离产生的五坐标 [Cr(TPP)(Cl)] 最初与 H2O 反应生成 [Cr(TPP)(Cl)( ) ]，最终将轴向 与 Py 交换以再生 [Cr(TPP)(Cl)(Py)]。发现 [Cr(TPP)(Cl)( )] 与外源 Py 的配体交换速率表现出钟形吡啶浓度依赖性。动力学研究表明，在高 Py 浓度下，外源 Py 可能与 [Cr(TPP)(Cl)( )] 的轴向 形成氢键，生成 [Cr(TPP)(Cl)(HO-H· ··Py)] 作为一个死胡同复合体。通过 X 射线结构分析确定了具有通过氢键与配位 配体结合的 2-甲基吡啶分子的 Cr-TPP 复合物
• Effect of a Sterically Hindered Imidazole Ligand on the Molecular Structure and Axial Ligand Substitution Reaction of the Chromium(III) Porphyrin Complex
  作者：Masahiko Inamo、Kiyohiko Nakajima

  DOI：10.1246/bcsj.71.883

  日期：1998.4

  A structural, thermodynamic, and kinetic study of a chromium(III) complex of 5,10,15,20-tetraphenylporphyrin, [Cr(tpp)(Cl)(L)], where L represents an imidazole ligand, is presented. The present study is aimed at elucidating the effect of a steric strain induced by the 2-methyl substituent of the imidazole ligand on the molecular structure and the dynamics of an axial ligand-substitution reaction. Crystals

  介绍了 5,10,15,20-四苯基卟啉 [Cr(tpp)(Cl)(L)] 的铬 (III) 配合物的结构、热力学和动力学研究，其中 L 表示咪唑配体。本研究旨在阐明由咪唑配体的 2-甲基取代基诱导的空间应变对分子结构和轴向配体取代反应动力学的影响。1-甲基咪唑配合物 [Cr(tpp)(Cl)(1-Meim)] (1) 和 1,2-二甲基咪唑配合物 [Cr(tpp)(Cl)(1,2-Me2im)] (2) 的晶体从二氯乙烷-甲苯混合物中获得，在单斜空间群 Cc, Z = 4, a = 18.306(2), b = 13.311(2), c = 21.391(5) A, β = 120.05(1)°, V = 4512(1) A3, 在正交空间群 P212121, Z = 4, a = 9.926(1), b = 17.902(3), c = 25.247(4) A, V = 4486(1)
• Effect of the axial halogen ligand on the substitution reactions of chromium(III) porphyrin complex
  作者：Kikuko Okada、Atsumi Sumida、Rie Inagaki、Masahiko Inamo

  DOI：10.1016/j.ica.2012.04.001

  日期：2012.9

  kinetics of the substitution reaction of the chromium(III) complex of 5,10,15,20-tetraphenylporphyrin, [Cr(TPP)(X)(L)] (X = F, Cl, Br), where L represents a non-charged ligand such as H2O, pyridine, or 1-methylimidazole, was investigated. The present study aimed to elucidate the effect of the axial halogen ligand, X on the substitution reaction of the ligand trans to X. The substitution reaction of the

  摘要5,10,15,20-四苯基卟啉[Cr（TPP）（X）（L）]（X = F，Cl，Br）的铬（III）配合物的取代反应的热力学和动力学，其中研究了L代表不带电荷的配体，例如H 2 O，吡啶或1-甲基咪唑。本研究旨在阐明轴向卤素配体X对配体向X的取代反应的影响。[Cr（TPP）（X）（Py）]的轴向吡啶配体被1-取代的反应在二氯甲烷中分光光度法研究了甲基咪唑，发现该反应是通过有限的离解机理进行的，并且对于氟络合物[Cr（TPP）（F）（Py）]，吡啶离解的活化焓要小得多。比氯络合物[Cr（TPP）（Cl）（Py）]，即ΔH‡= 57.5±1.1和97.2±1.4 kJ mol-1，分别。根据卤素配体对[Cr（TPP）（X）（L）]的轴向配体取代反应的反式作用来讨论这些结果，并得出结论，键的强度显示了Cr–的趋势。 F> Cr–Cl> Cr–Br，导致F−配体的强反式作用。
• Reactivity of Five-Coordinate Intermediate Generated by Laser Photolysis of Monoligated Chloro(5,10,15,20-tetraphenylporphinato)chromium(III) in Toluene
  作者：Masahiko Inamo、Mikio Hoshino、Kiyohiko Nakajima、Sen-ichi Aizawa、Shigenobu Funahashi

  DOI：10.1246/bcsj.68.2293

  日期：1995.8

  A, respectively. Laser irradiation of the toluene solution of [Cr(tpp)(Cl)(L)] causes the photodissociation of the axial ligand L, where L represents H2O or 3-cyanopyridine, to give the five-coordinate intermediate [Cr(tpp)(Cl)]. The rate constant of the axial ligand recombination reaction falls into a narrow range around 1 × 109 mol−1 kg s−1 at 25.0 °C for both reactions. The activation parameters

  对于两个反应，轴向配体重组反应的速率常数在 25.0 °C 时都落在 1 × 109 mol−1 kg s−1 左右的狭窄范围内。激活参数指示...
• Femtosecond time-resolved photo-absorption studies on the excitation dynamics of chromium(III) porphyrin complexes in solution
  作者：Masahiko Inamo、Chie Okabe、Takakazu Nakabayashi、Nobuyuki Nishi、Mikio Hoshino

  DOI：10.1016/j.cplett.2007.07.079

  日期：2007.9

  The electronic relaxation dynamics of the excited states of the chromium(III) tetraphenylporphyrin complexes, [Cr(TPP)(Cl)(L)] (L = H2O, pyridine, 1-methylimidazole), in toluene were studied by using femtosecond time-resolved absorption spectroscopy. The excited state (4T1) of 1-methylimidazole and pyridine complexes given by a very rapid intersystem crossing from 4S1 to 4T1 decays to establish the

  飞秒研究了铬（III）四苯基卟啉配合物[Cr（TPP）（Cl）（L）]（L = H 2 O，吡啶，1-甲基咪唑）在甲苯中的激发态电子弛豫动力学时间分辨吸收光谱。激发态（4 Ť 1 1-甲基咪唑），并从通过非常快速的系间窜越给予吡啶络合物4 š 1至4 Ť 1衰变来建立4 Ť 1  ⇌  6 Ť 1在几百皮秒平衡。的4 Ť 1个的[CR（TPP）（CL）（H状态2O）]表现出双指数衰减，该衰减由轴向H 2 O配体的光解离过程和[Cr（TPP）（Cl）]基态的光解中间产物的衰减组成。