| 188394-07-2

• CAS: 188394-07-2
• 化学式: C₄₆H₂₈Cl₄N₄O₂Ru
• 分子量: 911.636
• InChiKey: SATOYVLTOLDPNM-NBICUONBSA-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：

  、 以 二氯甲烷 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  Aziridination of Alkenes and Amidation of Alkanes by Bis(tosylimido)ruthenium(VI) Porphyrins. A Mechanistic Study

  摘要：

  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.

  DOI：

  10.1021/ja9913481

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