carbonylchloro[4-methyl-6-(N-p-chlorophenyliminiomethyl)phenolato-C(2),O]bis(triphenylphosphine)ruthenium(II) | 444017-93-0

• 英文名称: carbonylchloro[4-methyl-6-(N-p-chlorophenyliminiomethyl)phenolato-C(2),O]bis(triphenylphosphine)ruthenium(II)
• 英文别名: Ru(η2-C6H2O-2-CHNHC6H4Cl(p)-3-Me-5)(PPh3)2(CO)Cl；Carbon monoxide;2-[(4-chlorophenyl)iminomethyl]-4-methylbenzene-6-id-1-ol;chlororuthenium(1+);triphenylphosphane
• CAS: 444017-93-0
• 化学式: C₅₁H₄₁Cl₂NO₂P₂Ru
• 分子量: 933.816
• InChiKey: AJCPSDDBWQWUBF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.44
• 重原子数：
  59
• 可旋转键数：
  8
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  33.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  carbonylchloro[4-methyl-6-(N-p-chlorophenyliminiomethyl)phenolato-C(2),O]bis(triphenylphosphine)ruthenium(II) 、 sodium pyrrolidine-N-carbodithioate 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 3.0h， 以83%的产率得到
  参考文献：
  名称：

  结合亚胺-苯酚功能的二硫代氨基甲酸螯合钌有机金属的光谱、结构、电化学和细胞毒性研究

  摘要：

  摘要 [Ru(η2-RL)(PPh3)2(CO)Cl] (1) 与二硫代氨基甲酸二甲酯 (MeDTC)、二硫代氨基甲酸二乙酯 (EtDTC) 和吡咯烷二硫代氨基甲酸酯 (PyrDTC) 配体的钠盐的多相反应用于分离 [Ru(η1-RL)(PPh3)2(CO)(R'DTC)] (2(R)(R'DTC)) 类型的亮黄色结晶固体，其中 η2-RL 是 C6H2O-2 -CHNHC6H4R(p)-3-Me-5，η1-RL 为 C6H2OH-2-CHNC6H4R(p)-3-Me-5，R 为 Me、OMe、Cl，且 R' = Me、Et、Pyr。二硫代氨基甲酸酯配体的结合伴随着 Ru-O 和 Ru-Cl 键的解离，伴随着从亚胺-苯酚基团到亚胺-苯酚基序的质子转移。该反应还涉及到产品的旋转构象的空间控制变化。[Ru(η1-ClL)(PPh3)2(CO)(EtDTC)] (2(Cl)(EtDTC)) 的 X

  DOI：

  10.1080/00958972.2018.1550256
• 作为产物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 2-formyl-4-methyl-6-(p-chlorophenylaminomethylene)phenol 以 乙醇 为溶剂， 以82%的产率得到carbonylchloro[4-methyl-6-(N-p-chlorophenyliminiomethyl)phenolato-C(2),O]bis(triphenylphosphine)ruthenium(II)
  参考文献：
  名称：

  Acetylacetonato chelated ruthenium organometallics incorporating imine–phenol function: Spectroscopic, structural, electrochemical and cytotoxicity studies

  摘要：

  The heterogeneous phase reaction of Ru(eta(2)-RL)(PPh3)(2)(CO)Cl, 1 with lithium acetylacetonate (Liacac) afforded the complexes of the type Ru(eta(1)-RL)(PPh3)(2)(CO)(acac), 2 in excellent yield where eta(2)-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5 and eta(1)-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is H, Me, Cl. The chelation of acac is attended with the cleavage of Ru-O and Ru-Cl bonds and iminium-phenola-to -> imine-phenol prototropic shift. A sterically controlled change in rotational conformation is involved in the 1 -> 2 conversion. The conversion is irreversible and the type 2 species are thermodynamically more stable than the carboxylate, nitrite and nitrate complexes of 1. The crystal structures of Ru(eta(1)-MeL)(PPh3)(2)(CO)(acac), 2(Me) and Ru(eta(1)-ClL)(PPh3)(2)(CO)(acac), 2(Cl) are reported. Spectral (UV-Vis, IR, H-1 NMR) and electrochemical data of the complexes are also reported. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses. The complexes were also screened in vitro for their antiproliferative properties against the MCF-7 breast cancer cell lines by using the MTT assay. Flow cytometric analysis showed that the complexes arrested the cell cycle in the sub G0 phase. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2015.02.023

文献信息

• Pyridine-2-olato chelated ruthenium(II) organometallics incorporating imine-phenol function: spectroscopic, structural, electrochemical, and theoretical studies
  作者：Anikul Islam、Mrinal Kanti Ghosh、Suman Mondal、Paula Brandão、Swarup Chattopadhyay

  DOI：10.1080/00958972.2018.1550578

  日期：2019.1.2

  Abstract The heterogeneous phase reaction of excess sodium salt of 2-hydroxypyridine (OHpy) with [Ru(κ2C,O-RL)(PPh3)2(CO)Cl] (1) afforded complexes of the type [Ru(κ1C-RL)(PPh3)2(CO)(Opy)] (2) in excellent yield [κ2C,O-RL is 4-methyl-6-((N-R-arylimino)methyl)phenolato-C2,O), κ1C-RL is 4-methyl-6-((N-R-arylimino)methyl)phenol-C2) and R is H, Me, OMe, Cl]. The chelation of Opy is attended with the cleavage

  摘要 过量的 2-羟基吡啶 (OHpy) 钠盐与 [Ru(κ2C,O-RL)(PPh3)2(CO)Cl] (1) 的多相反应得到 [Ru(κ1C-RL) (PPh3)2(CO)(Opy)] (2) 以极好的收率 [κ2C,O-RL 是 4-methyl-6-((NR-arylimino)methyl)phenolato-C2,O), κ1C-RL 是 4 -甲基-6-((NR-芳基亚氨基)甲基)苯酚-C2)并且R是H、Me、OMe、Cl]。Opy的螯合伴随着Ru-O和Ru-Cl键的断裂和亚胺-苯酚→亚胺-苯酚的质子位移。1→2 转化是不可逆的，2 类物质在热力学上比 1 的乙酸盐、亚硝酸盐和硝酸盐配合物更稳定。报告了配合物的光谱（UV-vis、IR、NMR）和电化学数据。在二氯甲烷溶液中，配合物显示出一种准可逆的 RuIII/RuII 循环伏安响应，E1/2 范围为 0。65–0.69 V
• Metallacycle Expansion by Alkyne Insertion. Chemistry of a New Family of Ruthenium Organometallics
  作者：Kaushik Ghosh、Sujay Pattanayak、Animesh Chakravorty

  DOI：10.1021/om970917f

  日期：1998.5.1

  with carbonylchloro[4-methyl-6-((R-imino)methyl)phenolato-C,O]bis(triphenylphosphine)ruthenium(II), Ru(RL1)(PPh3)2(CO)Cl (3), affording the inserted product carbonylchloro[2-vinyl-4-methyl-6-((R-imino)methyl)phenolato-C,O]bis(triphenylphosphine)ruthenium(II), Ru(RL2,X)(PPh3)2(CO)Cl (4), in virtually quantitative yield. The X-ray structures of 4b (R = X = Ph) and 4g (R = Et, X = H) have revealed the presence

  乙炔和苯乙炔与羰基氯[4-甲基-6-（（R-亚氨基）甲基）苯酚基-C，O ]双（三苯基膦）钌（II），Ru（RL 1）（PPh 3）2（CO）Cl反应（3），得到插入的产物羰基氯[2-乙烯基-4-甲基-6-（（R-亚氨基）甲基）苯酚-C，O ]双（三苯基膦）钌（II），Ru（RL 2，X） （PPh 3）2（CO）Cl（4），实际上是定量的收率。4b（R = X = Ph）和4g（R = Et，X = H）的X射线结构表明存在扭曲的八面体RuC2 P 2 ClO协调领域。在3 → 4转换中，Ru（C，O）螯合环从四元膨胀为六元。苯乙炔的插入是区域特异性的，并提出了一个涉及初始Ru-O裂解和空间控制的反应模型。在RU-O键4比在显著较短（由~0.14 a）和更强3。这反映在钌（III）-钌（II）还原电位降低了约200 mV的情况下。N···O距离以及IR和NMR数据表明，4中未配位的席夫碱
• Chemistry of a new family of aryl ruthenium species incorporating α-diimine chelation and a pendant imine-phenol function
  作者：Bikash Kumar Panda、Kaushik Ghosh、Swarup Chattopadhyay、Animesh Chakravorty

  DOI：10.1016/s0022-328x(03)00211-0

  日期：2003.5

  The reaction of excess 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) with Ru(η2-RL)(PPh3)2(CO)Cl (1) has respectively furnished [Ru(η1-RL)(PPh3)2(CO)(bpy)](PF6) (2) and [Ru(η1-RL)(PPh3)2(CO)(phen)](PF6) (3) in very good yield (η2-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5, η1-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is H, Me, MeO, Cl). The chelation of bpy/phen is attended with the cleavage of RuO and

  的过量2,2'-联吡啶（BPY）和1,10-菲咯啉（phen）与钌（η反应2 -RL）（PPH 3）2（CO）Cl（上1）已分别提供的[Ru（η 1 -RL）（PPH 3）2（CO）（联吡啶）]（PF 6）（2）和的[Ru（η 1 -RL）（PPH 3）2（CO）（苯）]（PF 6）（3）在非常好的产率（η 2 -RL是C 6 H ^ 2 O-2-CHNHC 6 ħ 4 R（p）-3-ME-5，η 1个-RL是C 6H 2 OH-2-CHNC 6 H 4 R（p）-3-Me-5且R为H，Me，MeO，Cl。bpy / phen的螯合伴随RuO和RuCl键的裂解以及亚胺基苯酚基→亚胺基苯酚的质子转移。一氧化碳配位体位于顺式到酚氧在2和3相反在1。的晶体和分子结构的[Ru（η 1 -HL）（PPH 3）2（CO）（联吡啶）]（PF 6）·CH 2氯2（2（H）·CH 2氯2）和[茹（η 1
• Synthesis, Structure, and Properties of Biimidazole‐Chelated Arylruthenium Complexes
  作者：Bikash Kumar Panda、Suman Sengupta、Animesh Chakravorty

  DOI：10.1002/ejic.200300293

  日期：2004.1

  molecular structure of [Ru(η1-MeL)(PPh3)2(CO)(dmbi)](PF6)·CH2Cl2 is reported. For steric reasons the carbon monoxide ligand is located syn to the phenolic oxygen atom as opposed to anti in the precursor 1. In the hydrogen bonded imine-phenol function the O−H, H···N, and N···O distances are 0.83(8), 1.77(8), and 2.552(6) A, respectively, the O−H···N angle being 156(2)°. The Ru(dmbi) chelate along with

  通过使 Ru(η2-RL)(PPh3)2(CO)Cl (1) 与过量的 4,5-二甲基-2,2'-联咪唑 (dmbi) 反应，[Ru(η1-RL)(PPh3 )2(CO)(dmbi)](PF6) (2) 已以优异的产率分离（η2-RL 为 C6H2O-2-CHNHC6H4R(p)-3-Me-5，η1-RL 为 H-2-CHNC6H4R (p)-3-Me-5 且 R 是 Me、OMe 和 Cl)。在这个过程中，dmbi 配体经历五元螯合，亚胺-苯酚官能团互变异构为亚胺-苯酚官能团，席夫碱围绕 Ru-C 键进行大旋转。报道了[Ru(η1-MeL)(PPh3)2(CO)(dmbi)](PF6)·CH2Cl2 的晶体和分子结构。由于空间位阻原因，一氧化碳配体位于酚氧原子的顺侧，而不是前体中的反侧 1. 在氢键亚胺-苯酚官能团中，O-H、H…N 和 N…O 距离分别为 0.83(8)、1.77(8)
• Carbonylation of four-membered ruthenium and osmium metallacycles incorporating an orthometallated phenolic function: New acylruthenium and arylosmium complexes
  作者：Bikash Kumar Panda、Animesh Chakravorty

  DOI：10.1016/j.jorganchem.2005.04.012

  日期：2005.7

  The solution reaction of Ru(QL1)(PPh3)2(CO)Cl (3) and Os(QL1)(PPh3)2(CO)Br (4) with carbon monoxide at one atmosphere pressure has respectively afforded the orange acylruthenium system Ru(QL2)(PPh3)2(CO)Cl (5) and the yellow arylosmium dicarbonyl system Os(QL3)(PPh3)2(CO)2Br (6) in excellent yields. (QL1 is C6H2O-2-CHNHC6H4Q(p)-3-Me-5, QL2 is C6H2(CO-1)O-2-CHNHC6H4Q(p)-3-Me-5 and QL3 is C6H2OH-2-CHNC6H4Q(p)-3-Me-5

  在一个大气压下，Ru（QL 1）（PPh 3）2（CO）Cl（3）和Os（QL 1）（PPh 3）2（CO）Br（4）与一氧化碳的溶液反应分别得到橙色酰基钌体系Ru（QL 2）（PPh 3）2（CO）Cl（5）和黄色芳基二羰基芳烃Os（QL 3）（PPh 3）2（CO）2 Br（6），产率极高。（QL 1是C 6 H 2 O-2-CHNHC6 H 4 Q（p）-3-Me-5，QL 2为C 6 H 2（CO-1）O-2-CHNHC 6 H 4 Q（p）-3-Me-5和QL 3为C 6 H 2 OH-2-CHNC 6 H 4 Q（p）-3-Me-5并且Q为Me，OMe和Cl。）建议在3的情况下，形成类似于6的二羰基配合物作为中间体迅速经历芳基迁移并伴随酚配位提供5。6的稳定性这与in促进迁移反应的能力大大降低是一致的。在反应4  →  6中，Os–O（苯酚基）键被裂解，席夫碱部分经历亚胺基-苯