(carbonyl-κC)(methanol-κO)(5,10,15,20-tetra-p-tolylporphyrinato-κ(4)N)ruthenium(II) | 179930-29-1

• 英文名称: (carbonyl-κC)(methanol-κO)(5,10,15,20-tetra-p-tolylporphyrinato-κ(4)N)ruthenium(II)
• 英文别名: [Ru(5,10,15,20-tetra-p-tolylporphyrinato)(CO)(CH3OH)]；[Ru(5,10,15,20-tetra(tolyl)porphyrinate)(CO)(CH3OH)]；Ru(CO)(MeOH)(5,10,15,20-tetra-p-tolylporphyrinato)
• CAS: 179930-29-1
• 化学式: C₅₀H₄₀N₄O₂Ru
• 分子量: 829.963
• InChiKey: AAZNSEUIDZMBOJ-KDTBAHQYSA-N

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：

  (carbonyl-κC)(methanol-κO)(5,10,15,20-tetra-p-tolylporphyrinato-κ(4)N)ruthenium(II) 在 DBU 作用下， 以 二氯甲烷 为溶剂， 生成 chloride(nitrosyl)(meso-tetra-p-tolylporphyrinato)ruthenium(II)
  参考文献：
  名称：

  Synthesis and Axial Ligand Substitution Chemistry of Ru(TTP)(NO)X. Structures of Ru(TTP)(NO)X (X = ONO, OH)

  摘要：

  New complexes of the family Ru(TTP)(NO)X, where TTP = tetra-p-tolylporphyrinato dianion, and X = OMe, Cl, OH, SH, S-p-tolyl, O2CH, ONO, ONO2, N-3, or NCS, have been prepared by a variety of high-yield metathesis techniques from Ru(TTP)(CO)(MeOH). New complexes have been characterized by IR, NMR, and UV spectroscopies as well as by cyclic voltammetry, elemental analysis, and, in two cases, by X-ray crystallography. The two complexes which have been characterized by single-crystal X-ray diffraction, the hydroxide and nitrite complexes 6 and 10 both crystallize in the monoclinic space group P2(1)/n and have Z = 6, with two independent metalloporphyrins in the unit cell, one (ordered) lying on a general position and the other (disordered) with the ruthenium on an inversion center. Acid labilization of the methoxide results in facile substitution kinetics at room temperature and with the exception of the sulfhydryl complex, L = SH, the resulting complexes are air stable and thermally robust species. For example, the formate derivative cannot be decarboxylated thermally or photolytically to give a hydride complex, and the azido complex does not eliminate dinitrogen under similar conditions to give a nitrido complex.

  DOI：

  10.1021/ic980182m
• 作为试剂：
  描述：

  重氮乙酸乙酯 、 N-苯基马来酰亚胺 、 4-氯亚硝基苯 在 (carbonyl-κC)(methanol-κO)(5,10,15,20-tetra-p-tolylporphyrinato-κ(4)N)ruthenium(II) 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以87%的产率得到ethyl 2-(4-chlorophenyl)-4,6-dioxo-5-phenylhexahydro-2H-pyrrolo[3,4-d]isoxazole-3-carboxylate
  参考文献：
  名称：

  Diastereoselective ruthenium porphyrin-catalyzed tandem nitrone formation/1,3-dipolar cycloaddition for isoxazolidines. Synthesis, in silico docking study and in vitro biological activities

  摘要：

  钌酞菁催化了二氮化合物、亚硝基芳烃和烯烃的串联硝酮形成/1,3-极性环加成反应，生成的异噁唑烷具有良好至高的产率，以及卓越的区域、化学和立体选择性。这一方案适用于广泛的烯烃底物，并且各种功能团与反应条件兼容。计算机分析和体外生物实验揭示，本文合成的一些新异噁唑烷可能充当白三烯A4水解酶抑制剂。

  DOI：

  10.1039/c2ob26518d

文献信息

• Kinetics of C–H bond and alkene oxidation by trans-dioxoruthenium(<scp>VI</scp>) porphyrins
  作者：Clare Ho、Wa-Hung Leung、Chi-Ming Che

  DOI：10.1039/dt9910002933

  日期：——

  characterized, and the kinetics and mechanism of oxidation of the C–H bond and alkenes investigated. The complexes were selective towards tertiary C–H bonds in saturated alkanes but were almost inactive towards secondary C–H bonds. However, they were reactive towards aromatic hydrocarbons and the second-order rate constants (k2) for the oxidation of ethylbenzene and cumene by [Ru(tpp)O2](tpp = 5, 10, 15, 20-te

  A.合成并表征了一系列[Ru VI LO 2 ]配合物（H 2 L =对位取代的四苯基卟啉），并研究了C–H键和烯烃的氧化动力学和机理。该络合物对饱和烷烃中的C–H键具有选择性，但对C–H二级键几乎没有活性。但是，它们对芳烃有反应性，[Ru（tpp）O 2 ]（tpp = 5，10，15，20-四苯基卟啉）氧化乙苯和枯烯的二级速率常数（k 2）为2.21。 ×10 –4和3.16×10 –4 dm 3 mol –1s –1分别。发现环己烯被[Ru（tpp）O 2 ]烯丙基氧化的动力学同位素效应（K H / K D）为11.7 。CH 2 Cl 2 -MeOH混合物中烯烃氧化的主要有机产物是环氧化物，[Ru（tpp）O 2 ]得到的单体产物为[Ru IV（tpp）O]·EtOH。或[Ru IV（tpp）（OH）2 ·] EtOH。与[Ru VI（oep）O 2 ]（oep = 2,3,7,8
• Assemblies of Mixed-metal Hexaporphyrins with an Oxo-bridged Iron(III) Porphyrin Dimer in the Center
  作者：Masamitsu Suzuki、Kiyoshi Tsuge、Yoichi Sasaki、Taira Imamura

  DOI：10.1246/cl.2003.564

  日期：2003.7

  Four novel Fe-Ru mixed-metal hexaporphyrins having an Fe(III)-O-Fe(III) porphyrin dimer unit at the center and four surrounding ruthenium(II) porphyrin units were synthesized, characterized, and structurally analyzed by X-ray crystallography.

  合成、表征和结构分析了四种新型 Fe-Ru 混合金属六卟啉，其中心有一个 Fe(III)-O-Fe(III) 卟啉二聚体单元和四个周围的钌 (II) 卟啉单元.
• Structure and Properties of Carbonyl-Coordinated Ruthenium(II) and Osmium(II) Porphyrin Dimers Bridged by Aza Ligands
  作者：Chika Bando、Atsushi Furukawa、Kiyoshi Tsuge、Kazumi Takaishi、Yoichi Sasaki、Taira Imamura

  DOI：10.1246/bcsj.80.1955

  日期：2007.10.15

  Carbonyl-coordinated ruthenium(II) and osmium(II) porphyrin dimers bridged with aza ligands, [(M(por)-(CO)} 2 ](BL), (M = Ru II , Os II ; por = ttp (5,10,15,20-tetra-p-tolylporphyrinato dianion), oep (2,3,7,8,12,13,17,18-octa-ethylporphyrinato dianion); BL = pz (pyrazine), bpy (4,4'-bipyridine), dabco (1,4-diazabicyclo[2,2,2]octane)), were prepared and characterized, and their structures were determined

  尽管 Ru 络合物中的第一次氧化发生在卟啉环上，而 Os 络合物中的第一次氧化发生在金属中心。第一次氧化过程中电位分裂的程度反映了分子内氧化还原相互作用的大小，其顺序为：ttp > oep 和 Os（金属氧化）> Ru（环氧化），并且 dabco≥ pz≥ bpy。
• Aziridination of Alkenes and Amidation of Alkanes by Bis(tosylimido)ruthenium(VI) Porphyrins. A Mechanistic Study
  作者：Sze-Man Au、Jie-Sheng Huang、Wing-Yiu Yu、Wai-Hong Fung、Chi-Ming Che

  DOI：10.1021/ja9913481

  日期：1999.10.1

  Bis(tosylimido)ruthenium(VI) porphyrins, [Ru-VI(Por)(NTs)(2)] (Por TPP. TTP 4-Cl-TPP 4-MeO-TPP. OEP), were prepared in 60-74% yields by treatment of [Ru-II(Por)(CO)(MeOH)] with (N-(p-tolylsulfonyl)imino)phenyliodinane (PhI=NTs) in dichloromethane. In dichloromethane containing pyrazole, they reacted with alkenes or alkanes to give tosylamidoruthenium(IV) porphyrins, [Ru-IV(Por)(NHTs)(pz)], in about 75% yields. The reactions of [Ru-VI(TPP)(NTs)(2)] and [Ru-VI(OEP)(NTs)(2)] with styrene, para-substituted styrenes, norbornene, cyclooctene, and beta-methylstyrene afforded the corresponding N-tosylaziridines in 66-85% yields. The aziridination of cis-stilbene and cis-beta-methylstyrene by [Ru-VI(Por)(NTs)(2)] is nonstereospecific with a partial loss of the alkene stereochemistry. Kinetic studies on the reactions between [Ru-VI(TPP)(NTs)(2)] and 16 alkenes (cyclooctene, norbornene, 2,3-dimethyl-2-butene, styrene, para-substituted styrenes, alpha- and beta-methylstyrene, and alpha- and beta-deuteriostyrene) gave the second-order rate constants (k(2)) ranging from (1.60 +/- 0.06) x 10(-3) to (90 +/- 4) x 10(-3) dm(3) mol(-1) s(-1) at 298 K. The slope of the linear plot of log k(2) vs E-1/2 for eight representative alkenes was found to be -1.7 V-1. Tn the case of para-substituted styrenes, linear correlation between log k(R) (k(R) = relative rate) and sigma(+) gives a rho(+) value as small as -1.1. However, the effect of para substituents on k(R) can be best accounted for by considering both the polar and spin delocalization effect. Measurements on the secondary deuterium isotope effect revealed that only the beta-carbon atom of styrene experienced a significant change in its hybridization in reaching the transition state. All these are consistent with rate-determining formation of a carboradical intermediate. The reactions of [Ru-VI(TPP)(NTs)(2)] and [Ru-VI(OEP)(NTs)(2)] with adamantane, cyclohexene, ethylbenzene, and cumene resulted in tosylamidation of these hydrocarbons and afforded the corresponding amides in 52-88% yields. For cyclohexane and toluene, the tosylamidation products were formed in poor yields (ca. 10%). Kinetic studies on the reactions between [Ru-VI(TPP)(NTs)(2)] and nine hydrocarbons (cumene, ethylbenzene, cyclohexene, and para-substituted ethylbenzenes) gave the second-order rate constants (k(2)) in the range of (0.330 +/- 0.008) x 10(-3) to (16.5 +/- 0.3) x 10(-3) dm(3) mol(-1) s(-1). These reactions exhibit a large primary deuterium isotope effect, with a k(H)/k(D) ratio of 11 for the tosylamidation of ethylbenzene. In the case of para-substituted ethylbenzenes, both electron-donating and -withdrawing substituents moderately promote the reaction. There is an excellent linear correlation between log k(R) and a related carboradical parameter. On the basis of these observations, a mechanism involving the rate-limiting formation of a carboradical intermediate is postulated.
• Synthesis and Characterization of Isostructural Metalloporphyrin Chalconitrosyl Complexes Ru(TTP)(NE)Cl (E = O, S) and a Remarkable Thionitrosyl/Nitrite → Nitrosyl/Thiazate Transformation
  作者：D. Scott Bohle、Chen-Hsiung Hung、Annie K. Powell、Bryan D. Smith、Sigrid Wocadlo

  DOI：10.1021/ic9614576

  日期：1997.5.1

  When Ru(TP)(NS)Cl is treated with silver nitrite, the product is not the expected halide metathesis product but a N-bound thiazate complex.