Thioether-ligated iron(II) and iron(III)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere.
نویسندگان
چکیده
The non-heme iron complexes, [Fe(II)(N3PySR)(CH3CN)](BF4)2 () and [Fe(II)(N3Py(amide)SR)](BF4)2 (), afford rare examples of metastable Fe(iii)-OOH and Fe(iii)-OOtBu complexes containing equatorial thioether ligands and a single H-bond donor in the second coordination sphere. These peroxo complexes were characterized by a range of spectroscopic methods and density functional theory studies. The influence of a thioether ligand and of one H-bond donor on the stability and spectroscopic properties of these complexes was investigated.
منابع مشابه
Differences and Comparisons of the Properties and Reactivities of Iron(III)–hydroperoxo Complexes with Saturated Coordination Sphere
Heme and nonheme monoxygenases and dioxygenases catalyze important oxygen atom transfer reactions to substrates in the body. It is now well established that the cytochrome P450 enzymes react through the formation of a high-valent iron(IV)-oxo heme cation radical. Its precursor in the catalytic cycle, the iron(III)-hydroperoxo complex, was tested for catalytic activity and found to be a sluggish...
متن کاملElectronic property and reactivity of (hydroperoxo)metal compounds.
DFT calculations were done for the (hydroperoxo)metal complexes with eta1-coordination mode, where metal ions are Fe(III), Al(III), Cu(II) and Zn(II). Results shows that 1) the electron density at the two oxygen atoms of the hydroperoxide ion is highly dependent on the angle O-O-H in M-OOH species and the difference in electron density between the two oxygen atoms reaches a maximum at the angle...
متن کاملSecondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH3)](BF4)2 (3) and [Fe(II)(N4Py(2Ph,amide))](BF4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative Fe(IV)(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide sub...
متن کاملSynthesis, Characterization, Electrochemical and Spectroelectrochemical Properties of Ruthenium(II) Complexes Containing Phenylcyanamide Ligands and Effect of the Inner- Sphere on the Ru-NCN Chromophore
[Ru(terpy)(bpy)(L)]PF6 complexes, where terpy is 2,2΄:6′,2″– terpyridine, bpy is 2,2΄ - bipyridine and L is monoanions of 4 - bromophenylcyanamide (4 - Brpcyd), 4-methoxyphenylcyanamide (4 - MeOPcyd), 2, 4 - dibromophenylcyanamide (2,4 - Br2pcyd), 2,4-dimethylphenylcyanamide (2,4 - Me2pcyd), 2 - methylphenylcyanamide (2 ...
متن کاملSYNTHESIS AND CHARACTERIZATION OF MONO AND BIS HEXAMETHYLENETETRAMINE IRON(II1) CHLORIDE IN NONAQUEOUS SOLVENT (CHCI )
Mono and bis hexamethylenetetramine iron(III) chloride, Fe(N C ,H ) CI (I) and Fe(N C ,H ) Cl (II) were synthesized by the reaction of iron(III) chloride and hexamethylenetetramine (HMTA) in chloroform. Chemical analysis and spectral results show the coordination of HMTA to the iron(III). Electronic transition spectra of compound I and I1 were also studied in coordinating and noncoordinatin...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Dalton transactions
دوره 43 20 شماره
صفحات -
تاریخ انتشار 2014