78668-28-7Relevant articles and documents
Catalytic Selective Oxidation of Primary and Secondary Alcohols Using Nonheme [Iron(III)(Pyridine-Containing Ligand)] Complexes
Caselli, Alessandro,Gallo, Emma,Panza, Nicola,Rizzato, Silvia,Tseberlidis, Giorgio,di Biase, Armando
supporting information, p. 6635 - 6644 (2020/10/30)
The selective oxidation of different primary and secondary alcohols to carbonyl compounds by hydrogen peroxide was found to be catalyzed in conversion ranging from good to excellent by an iron(III) complex of a pyridine-containing macrocyclic ligand (Pc-L), without the need of any additive. The choice of the counteranion (Cl, Br, OTf) appeared to be of fundamental importance and the best results in terms of selectivity (up to 99 %) and conversion (up to 98 %) were obtained using the well-characterized [Fe(III)(Br)2(Pc-L)]Br complex, 4c. Magnetic moments in solid-state, also confirmed in solution ([D6]DMSO) by Evans NMR method, were calculated and point out to an iron metal center in the high spin state of 5/2. The crystal structure shows that the iron(III) center is coordinated by the four nitrogen atoms of the macrocycle and two bromide anions to form a distorted octahedral coordination environment. The catalytic oxidation of benzyl alcohol in acetonitrile was found occurring with better conversions and selectivities than in other solvents. The reaction proved to be quite general, tolerating aromatic and aliphatic alcohols, although very low yields were obtained for terminal aliphatic alcohols. Preliminary mechanistic studies are in agreement with a catalytic cycle promoted by a high-spin iron complex.
A zinc-tetraazatricyclo complex, a preparing method thereof and applications of the complex in antitumor drugs
-
, (2017/04/28)
A zinc-tetraazatricyclo complex, a preparing method thereof and applications of the complex in antitumor drugs are disclosed. The structure formula of the complex CHN5O3ZnCl(L-Zn) is shown as a formula 1. The Zn-tetraazatricyclo complex has good DNA hydrolysis and cutting activity. Influences of the Zn-tetraazatricyclo complex on cell propagation of cancer cell strains, normal cell strains and cell strains having drug resistance to cis-platinum are researched by applying an MTT process and by adopting the cis-platinum as a positive contrast medicine, and results show that the a cell propagation inhibiting function of the Zn-tetraazatricyclo complex is better than that of the cis-platinum, and toxicity of the complex to normal liver cells is slightly lower than that to liver cancer cells. In-vivo tumor proliferation inhibiting activity of the Zn-tetraazatricyclo complex is researched by utilizing an ICR mouse model with subcutaneous implantation of H22 liver cancer cells, and results show that the Zn-tetraazatricyclo complex has good tumor proliferation inhibiting activity.
Exceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron species
Serrano-Plana, Joan,Aguinaco, Almudena,Belda, Raquel,García-Espa?a, Enrique,Basallote, Manuel G.,Company, Anna,Costas, Miquel
supporting information, p. 6310 - 6314 (2016/05/24)
The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at -40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies. The observed fast reaction rates and high selectivities demonstrate that this metastable compound is a truly competent OAT intermediate of relevance for nonheme iron catalyzed epoxidations. A metastable nonheme iron-oxygen species undergoes exceedingly fast oxygen atom transfer (OAT) to olefins, providing epoxides with stereoretention. The reaction rates determined by stopped-flow UV/Vis analysis are in good agreement with the relative reactivities of different olefins, confirming that this compound is a competent OAT intermediate of relevance to nonheme iron catalyzed epoxidations.