دورية أكاديمية
Apically linked iron(II) α-dioximate and α-oximehydrazonate bis-clathrochelates: synthesis, structure and electrocatalytic properties.
| العنوان: | Apically linked iron(II) α-dioximate and α-oximehydrazonate bis-clathrochelates: synthesis, structure and electrocatalytic properties. |
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| المؤلفون: | Belaya IG; Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia., Svidlov SV, Dolganov AV, Zelinskii GE, Potapova TV, Vologzhanina AV, Varzatskii OA, Bubnov YN, Voloshin YZ |
| المصدر: | Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2013 Oct 07; Vol. 42 (37), pp. 13667-78. Date of Electronic Publication: 2013 Aug 01. |
| نوع المنشور: | Journal Article; Research Support, Non-U.S. Gov't |
| اللغة: | English |
| بيانات الدورية: | Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 101176026 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1477-9234 (Electronic) Linking ISSN: 14779226 NLM ISO Abbreviation: Dalton Trans Subsets: MEDLINE |
| أسماء مطبوعة: | Original Publication: Cambridge, UK : Royal Society of Chemistry, c2003- |
| مواضيع طبية MeSH: | Ferrous Compounds/*chemical synthesis , Ferrous Compounds/*chemistry , Hydrazones/*chemistry , Oximes/*chemistry, Catalysis ; Electrochemical Techniques ; Models, Molecular ; Molecular Structure |
| مستخلص: | Iron(II) α-oximehydrazonate and α-dioximate bis-clathrochelates with apical hydrocarbon linkers were obtained by template condensation on an iron(II) ion followed by H(+)-catalyzed macrobicyclization of the bis-semiclathrochelate precursor with formaldehyde and triethyl orthoformate, and by transmetallation of the triethylantimony-containing clathrochelate precursor with diboron-containing bifunctional Lewis acids, respectively. The geometry of the para-phenylenediboron-capped iron(II) bis-clathrochelate studied by single-crystal X-ray diffraction is intermediate between a trigonal prism and a trigonal antiprism with a distortion angle of 20.4°; the rigidity of its C6H4 linker results in the presence of the expected three-fold pseudo-rotational B···Fe···B···B···Fe···B axis and a staggered conformation of the cyclohexane-containing chelate moieties. The cyclic voltammograms (CVs) for the oximehydrazonate bis-clathrochelates contain single one-electron (for each metallocentre, and therefore, two electrons per molecule) quasi-reversible reduction waves assigned to the redox-processes of Fe(2+/+), and no interaction is observed between the two encapsulated iron(I)-containing metallocenters; six strong electron-withdrawing ethoxy substituents in the 1,3,5-triazacyclohexane capping fragments substantially affect the potential of this reduction. The corresponding waves for the dioximate complexes are irreversible: due to the structural rigidity of the caging tris-dioximate ligands, their reduced dianionic forms are unstable on the CV time scale. The CV for the hexaethoxy bis-clathrochelate complex contains one two-electron reversible oxidation wave assigned to the metal-centered oxidation of Fe(2+/3+), whereas those for its dioximate analogs are quasi-reversible. The relative lability of the ligand cavity in binuclear oximehydrazonates causes a stabilization of both the oxidized and the reduced forms; the reduced iron(I)-containing species are highly electrocatalytically active in the hydrogen-producing 2H(+)/H2 reaction. Their higher activity as compared with that for dioximate bis-clathrochelates was explained by the higher availability of the catalytically active metallocentres for H(+) ions. |
| المشرفين على المادة: | 0 (Ferrous Compounds) 0 (Hydrazones) 0 (Oximes) |
| تواريخ الأحداث: | Date Created: 20130802 Date Completed: 20140328 Latest Revision: 20130903 |
| رمز التحديث: | 20240628 |
| DOI: | 10.1039/c3dt50881a |
| PMID: | 23903469 |
| قاعدة البيانات: | MEDLINE |
Full Text Finder | تدمد: | 1477-9234 |
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| DOI: | 10.1039/c3dt50881a |