cis-[Ru(4,7-dimethyl-1,10-phenanthroline)₂Cl₂] | 76514-76-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: cis-[Ru(4,7-dimethyl-1,10-phenanthroline)₂Cl₂]
• 英文别名: bis(4,7-dimethyl-1,10-phenanthroline)dichlororuthenium(II)；Ru(4,7-dimethyl-1,10-phenanthroline)2Cl2；Ru(II)(4,7-dimethyl-1,10-phenanthroline)2Cl2；[Ru(Me2phen)2Cl2]；dichlororuthenium;4,7-dimethyl-1,10-phenanthroline
• CAS: 76514-76-6
• 化学式: C₂₈H₂₄Cl₂N₄Ru
• 分子量: 588.501
• InChiKey: LOIYFJUKYFDWEO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.18
• 重原子数：
  35
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cis-[Ru(4,7-dimethyl-1,10-phenanthroline)₂Cl₂] 、 1,2-双(4'-甲基-2,2'-联吡啶-4-基)乙烷 在 ammonium hexafluorophosphate 作用下， 以 甲醇 为溶剂， 生成 Ru(4,7-dimethyl-1,10-phenanthroline)2{1,2-bis(4-(4'-methyl-2,2'-bipyridyl))ethane}(PF6)2
  参考文献：
  名称：

  Four Intercomponent Processes in a Ru(II)-Rh(III) Polypyridine Dyad: Electron Transfer from Excited Donor, Electron Transfer to Excited Acceptor, Charge Recombination, and Electronic Energy Transfer

  摘要：

  The binuclear complex Ru-II(Me(2)phen)(2)-(Mebpy-CH2-CH2-Mebpy)-Rh-III(Me(2)pby)(2)(5+) (Me(2)phen = 4,7-dimethyl-1,10- phenanthroline; Mebpy = 4-methyl-2,2'-bipyridine; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine), hereafter represented by Ru(II)-Rh(III), was synthesized and studied. Selective excitation of the two moieties of the dyad was achieved with visible (100% *Ru(II)-Rh(III)) or ultraviolet light (e.g., at 298 nm, 70% Ru(II)-*Rh(III)), In room-temperature fluid solutions, both local excited states are quenched by electron transfer, leading to a common Ru(III)-Rh(II) state. The two forward electron-transfer processes, as well as the recombination process leading back to the ground state, can be resolved by transient laser spectroscopy, using various excitation wavelengths and pulse widths (532 nm, 30 ps; 427 nm, 0.5 ps; 298 nm, 0.5 ps). Rate constants in acetonitrile are as follows: *Ru(II)-Rh(III) --> Ru(III)-Rh(II), 1.7 X 10(8) s(-1); Ru(II)-*Rh(III) --> Ru(III)-Rh(II), 3.3 x 10(10) s(-1); Ru(III)-Rh(II) --> Ru(II)-Rh(III), 7.1 x 10(9) s(-1). The rate constants can be rationalized in terms of standard electron-transfer theory, assuming that the driving force (Delta G degrees =-0.10, -0.70, and -2.07 eV, respectively) is the main variable parameter. The two forward processes belong to the ''normal'', and the back reaction belongs to the ''inverted'' free-energy regime. In room-temperature fluid solution, no Ru(II)-*Rh(III) --> *Ru(II)-Rh(III) energy transfer (Delta G degrees =-0.61 eV) is observed, presumably because of efficient competition by the faster Ru(II)-*Rh(III) --> Ru(III)-Rh(II) electron-transfer quenching. By contrast, this process becomes efficient in rigid media (room-temperature or 77 K), where both the *Ru(II)-Rh(III) --> Ru(III)-Rh(II) and Ru(II)-*Rh(III) --> Ru(III)-Rh(II) electron-transfer processes are blocked as a consequence of restricted solvent repolarization. In 77 K ethanol glass, the energy-transfer rate constant is 1.9 X 10(6) s(-1).

  DOI：

  10.1021/ja00088a013
• 作为产物：
  描述：

  4,7-二甲基-1,10-菲咯啉 、 dichloro(1,5-cyclooctadiene)ruthenium(II) 以 邻二氯苯 为溶剂， 反应 3.0h， 以27%的产率得到cis-[Ru(4,7-dimethyl-1,10-phenanthroline)₂Cl₂]
  参考文献：
  名称：

  钌催化 C-H 羟基化的机理研究揭示了一种意想不到的催化剂阻滞途径

  摘要：

  我们最近公开了 [(dtbpy)2RuCl2] 作为 C(sp3)-H 键化学选择性 CH 羟基化的有效预催化剂，并注意到 4,4'-二叔丁基-2,2 之间的反应性能存在显着差异'-联吡啶 (dtbpy)- 和 2,2'-联吡啶 (bpy)-衍生的复合物。了解这种差异的起源并进一步推进这种催化方法的愿望推动了本文所述的综合机理研究。通过评估配体结构-活性关系、电化学和动力学研究以及加压样品注入高分辨率质谱 (PSI-MS)，已经揭示了该反应的细节。本次调查的显着发现包括确定了不止一种活性氧化剂和三种不同的催化剂分解/阻滞机制。催化剂效率，以转换数衡量，与配体解离的速率和程度有很强的负相关，这取决于联吡啶 4,4'-取代基的身份。解离的联吡啶配体在反应条件下被氧化为单和双 N-氧化物物质，发现前者充当有效的催化剂毒物，产生催化惰性的三连接 [Ru(dtbpy)2(dtbpy N -氧化物)]2+

  DOI：

  10.1021/jacs.8b10950

文献信息

• Long range photoinduced electron transfer in a rigid polymer
  作者：Tom Guarr、Mark E. McGuire、George McLendon

  DOI：10.1021/ja00304a015

  日期：1985.9

  Etude de la desactivation d'une serie de complexes de Ru(II) par des amines aromatiques dans un film de polycarbonate de bisphenol A

  练习曲 de la desactivation d'une serie de complexes de Ru(II) par des aminesaromatiques dans un film de polycarbonate de bisphenol A
• Meso-[{Ru(phen)2}2(μ-bpm)]4+: A high-affinity DNA bulge probe {bpm=2,2′-bipyrimidine; phen=1,10-phenanthroline}
  作者：Joy L. Morgan、Damian P. Buck、Adam G. Turley、J. Grant Collins、F. Richard Keene

  DOI：10.1016/j.ica.2005.06.036

  日期：2006.2

  The binding of the stereoisomers of [Ru(Me2bpy)2}2(μ-bpm)]4+, [Ru(phen)2}2(μ-bpm)]4+ and [Ru(Me2phen)2}2(μ-bpm)]4+ (Me2bpy = 4,4′-dimethyl-2,2′-bipyridine; bpm = 2,2′-bipyrimidine; phen = 1,10-phenanthroline; Me2phen = 4,7-dimethyl-1,10-phenanthroline) to a tridecanucleotide d(CCGAGAATTCCGG)2 which contains a single adenine bulge site, and four control dodecanucleotides, have been studied using a

  [Ru（Me 2 bpy）2 } 2（μ-bpm）] 4+，[Ru（phen）2 } 2（μ-bpm）] 4+和[Ru（Me 2 phen）2 } 2（μ-bpm）] 4+（Me 2 bpy = 4,4'-二甲基-2,2'-联吡啶; bpm = 2,2'-联嘧啶; phen = 1,10-菲咯啉; Me已使用荧光嵌入剂置换（FID）分析法研究了2个phen = 4,7-二甲基-1,10-菲咯啉）到一个13核苷酸d（CCGAGAATTCCGG）2（其中包含一个腺嘌呤凸起位点和4个对照十二核苷酸）。中观[Ru（phen）2 } 2（μ-bpm）] 4+的异构体显示出与包含凸起的十三核苷酸的最强结合。为了更好地理解内消旋异构体对凸出序列表现出的更高亲和力的基础，对rac -[Ru（phen））的两个对映异构体（ΔΔ和ΛΛ）的结合进行了1 H NMR研究2 } 2（μ-bpm）] 4+，
• Necroptosis Induced by Ruthenium(II) Complexes as Dual Catalytic Inhibitors of Topoisomerase I/II
  作者：Kai Xiong、Chen Qian、Yixian Yuan、Lin Wei、Xinxing Liao、Liting He、Thomas W. Rees、Yu Chen、Jian Wan、Liangnian Ji、Hui Chao

  DOI：10.1002/anie.202006089

  日期：2020.9.14

  reported. Ruthenium(II) complexes containing 1,1‐(pyrazin‐2‐yl)pyreno[4,5‐e][1,2,4]triazine were developed with a series of different ancillary ligands (Ru1‐7). The combination of the main ligand with bipyridyl and phenylpyridyl ligands endows Ru7 with superior nucleus‐targeting properties. As a rare dual catalytic inhibitor, Ru7 effectively inhibits the endogenous activities of topoisomerase (topo) I and

  在癌细胞中诱导坏死病是一种规避耐药性的有效方法。但是，很少有基于金属的触发器的报道。钌（II）含有1,1-（吡嗪-2-基）络合物pyreno [4,5-E] [1,2,4]三嗪用一系列不同的辅助配体（开发RU1 - 7）。主配体与联吡啶和苯基吡啶基配体的结合赋予Ru7优越的核靶向性能。作为一种罕见的双重催化抑制剂，Ru7有效抑制拓扑异构酶（拓扑）I和II的内源性活性，并通过坏死性杀伤癌细胞。阐明了从拓扑抑制到坏死病的细胞信号通路。此外，Ru7在体内对耐药性癌细胞具有显着的抗肿瘤活性。据我们所知，Ru7是第一种基于Ru的坏死病诱导化疗药物。
• Emission Tuning of Heteroleptic Arylborane–Ruthenium(II) Complexes by Ancillary Ligands: Observation of Strickler–Berg-Type Relation
  作者：Atsushi Nakagawa、Akitaka Ito、Eri Sakuda、Sho Fujii、Noboru Kitamura

  DOI：10.1021/acs.inorgchem.8b01058

  日期：2018.8.6

  Novel heteroleptic arylborane–ruthenium(II) complexes having a series of ancillary ligands L′ ([Ru(B2bpy)L′2]2+) in CH3CN showed low-energy/intense metal-to-ligand charge transfer (MLCT)-type absorption and intense/long-lived emission compared to the reference complexes. The spectroscopic and photophysical properties of [Ru(B2bpy)L′2]2+ were shown to be manipulated synthetically by the electron-donating

  在CH 3 CN中具有一系列辅助配体L'（[Ru（B 2 bpy）L' 2 ] 2+）的新型杂芳基硼烷-钌（II）配合物显示出低能/强金属-配体电荷转移（ MLCT）型吸收和强烈/长寿命发射（与参比配合物相比）。已显示[Ru（B 2 bpy）L' 2 ] 2+的光谱和光物理性质是通过辅助配体的供电子能力综合控制的。在CH 3中观察到[Ru（B 2 bpy）L' 2 ] 2+的强烈且长寿命发射298 K处的CN负责加速辐射和减速非辐射衰变过程，这些过程可通过辅助配体的电子结构控制。此外，在本系统研究的基础上，我们成功地证明了MLCT谱带的摩尔吸收系数与配合物的辐射速率常数之间的Strickler-Berg型关系。
• Photoinduced Electron Transfer across Oligo-<i>p</i>-phenylene Bridges. Distance and Conformational Effects in Ru(II)−Rh(III) Dyads
  作者：Maria Teresa Indelli、Claudio Chiorboli、Lucia Flamigni、Luisa De Cola、Franco Scandola

  DOI：10.1021/ic700430u

  日期：2007.7.1

  series of rodlike ruthenium(II)-rhodium(III) polypyridine dyads based on modular oligo-p-phenylene bridges, of the general formula [(Me2phen)2Ru-bpy-(ph)n-bpy-Rh(Me2bpy)]5+ (Me2phen=4,7-dimethyl-1,10-phenanthroline; bpy=2,2'-bipyridine; ph=1,4-phenylene; n=1-3), have been synthesized and their photophysical properties investigated. The dyad [(Me2bpy)2Ru-bpy-(ph)3'-bpy-Rh(Me2bpy)]5+ with the central

  基于通式[（Me2phen）2Ru-bpy-（ph）n-bpy-Rh（Me2bpy）] 5的一系列基于模块化低聚对亚苯基桥的棒状钌（II）-铑（III）聚吡啶二联体+（Me2phen = 4,7-二甲基-1,10-菲咯啉; bpy = 2,2'-联吡啶; ph = 1,4-亚苯基; n = 1-3），并对其光物理性质进行了研究。还研究了带有中心亚苯基带有两个己基链的二元[（Me2bpy）2Ru-bpy-（ph）3'-bpy-Rh（Me2bpy）] 5+。对于该系列中最长（n = 3）的垫片，金属到金属的距离达到24A。对于室温CH3CN溶液中的所有二元组，观察到Ru基发色单元的典型金属到配体电荷转移发光的猝灭，这表明发生了从激发的Ru部分到Rh基单元的分子内光诱导电子的有效转移。通过纳秒和皮秒级的时间分辨发射和吸收光谱法确定了电子转移过程的速率常数。观察到实验传输速率对桥长度的指数依赖性，