Assessing the Impact of Electronic and Steric Tuning of the Ligand in the Spin State and Catalytic Oxidation Ability of the FeII(Pytacn) Family of Complexes was written by Prat, Irene;Company, Anna;Corona, Teresa;Parella, Teodor;Ribas, Xavi;Costas, Miquel. And the article was included in Inorganic Chemistry in 2013.Related Products of 315180-16-6 This article mentions the following:
A family of iron complexes [FeII(R,R’Pytacn)(X)2]n+ is described, where R,R’Pytacn is the tetradentate ligand 1-[(4-R’-6-R-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, where R refers to the group at the α-position of the pyridine, R’ corresponds to the group at the γ-position, and X denotes MeCN or CF3SO3. Herein, the authors study the influence of the pyridine substituents R and R’ on the electronic properties of the coordinated Fe center by a combination of structural and spectroscopic characterization using x-ray diffraction, 1H NMR and UV-visible spectroscopies, and magnetic susceptibility measurements. The electronic properties of the substituent in the γ-position of the pyridine ring (R’) modulate the strength of the ligand field, as shown by magnetic susceptibility measurements in CD3CN solution, which provide a direct indication of the population of the magnetically active high-spin S = 2 ferrous state. Indeed, complexes [FeII(H,R‘Pytacn)(CD3CN)2]2+ exist as mixtures of high-spin (S = 2) and low-spin (S = 0) complexes, and their effective magnetic moment directly correlates with the electron-releasing ability of R’. However, the substitution of the H atom in the α-position of the pyridine by a Me, Cl, or F group favors the high-spin state. The whole family of complexes was assayed in catalytic C-H and C=C oxidation reactions with H2O2. These catalysts exhibit excellent efficiency in the stereospecific hydroxylation of alkanes and in the oxidation of olefins. Remarkably, R’-substituents have little influence on the efficiency and chemoselectivity of the catalytic activity of the complexes, but the selectivity toward olefin cis-dihydroxylation is enhanced for complexes with R = Me, F, or Cl. Isotopic labeling studies in the epoxidation and cis-dihydroxylation reactions show that R has a definitive role in dictating the origin of the O atom that is transferred in the epoxidation reaction. In the experiment, the researchers used many compounds, for example, 2-(Chloromethyl)-6-fluoropyridine (cas: 315180-16-6Related Products of 315180-16-6).
2-(Chloromethyl)-6-fluoropyridine (cas: 315180-16-6) belongs to pyridine derivatives. In contrast to benzene, Pyridine’s electron density is not evenly distributed over the ring, reflecting the negative inductive effect of the nitrogen atom. Pyridine, its benzo and pyridine-based compounds play diverse roles in organic chemistry. Pyridine-based materials are valued for their optical and physical properties as well as their medical potential. Related Products of 315180-16-6