Unexpected Formation of Fe II Fe III Fe II - and Fe II Fe II Fe II -trinuclear Hexapyridineoximate Helicates: Synchrotron Single-Crystal X-ray Structures | Sciact - CRIS-system of Boreskov Institute of Catalysis

Unexpected Formation of Fe II Fe III Fe II - and Fe II Fe II Fe II -trinuclear Hexapyridineoximate Helicates: Synchrotron Single-Crystal X-ray Structures Full article

Journal

Russian Journal of Coordination Chemistry
ISSN: 1070-3284 , E-ISSN: 1608-3318

Output data

Year: 2024, Volume: 77, Number: 11, Pages: 1285-1294 Pages count : 10 DOI: 10.1080/00958972.2024.2338528

Tags

Iron complexes; polynuclear complexes; helicates; X-ray diffraction analysis; synchrotron studies

Authors

Belov Alexander S. ^1,2 , Belova Svetlana A. ^1,2 , Danshina Anastasia A. ^1,3 , Zubavichus Yan V. ⁴ , Bugaenko Margarita G. ¹ , Voloshin Yan Z. ^1,2

Affiliations

1	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
2	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
3	Moscow Institute of Physics and Technology (National Research University), Dolgoprudny, Russia
4	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Koltsovo, Russia

Template condensation of 2-acetylpyridineoxime with butyl ester of 1,3-propanediboronic acid in the presence of iron(II) affords a poorly separable mixture of complex products. Similar results were observed when Fe3+ ions were used for cross-linking in place of the diboronic acid. Prolonged crystallization of these mixtures gave crystals of perchlorate salts of a FeIIFeIIIFeII-trinuclear hexapyridineoximate cation and of an analogous FeIIFeIIFeII-intracomplex that crystallize with chloroform and dichloromethane solvent molecules, respectively. Both complexes were characterized by synchrotron single-crystal X-ray diffraction (XRD) experiments. The Fe–N distances of the two ‘terminal’ iron cations are virtually the same between these trinuclear complexes and unambiguously support assignments of oxidation number +2 and low-spin state (S = 0). The centers of the FeN6-coordination polyhedra adopt geometries resembling trigonal antiprisms with distortion angles φ of approximately 40°. The FeO6-coordination polyhedra possess an almost ideal Oh geometry with φ close to 60°. Each of these iron(II) or iron(III) µ3-metallocenters acts as a bifunctional Lewis acid that cross-links two pseudoclathrochelate entities, formed by the ‘terminal’ iron(II) ions, to give an almost linear (the corresponding intramolecular Fe(2)…Fe(1)…Fe(3) angles are close to 180°) helical cation or intracomplex

Belov A.S. , Belova S.A. , Danshina A.A. , Zubavichus Y.V. , Bugaenko M.G. , Voloshin Y.Z.
Unexpected Formation of Fe II Fe III Fe II - and Fe II Fe II Fe II -trinuclear Hexapyridineoximate Helicates: Synchrotron Single-Crystal X-ray Structures
Russian Journal of Coordination Chemistry. 2024. V.77. N11. P.1285-1294. DOI: 10.1080/00958972.2024.2338528 WOS Scopus AN OpenAlex publication_identifier_short.sciact_skif_identifier_type

Accepted:	Mar 4, 2023
Submitted:	Dec 12, 2023
Published online:	Apr 11, 2024

Web of science:	WOS:001200775700001
Scopus:	2-s2.0-85190560229
Chemical Abstracts:	2024:809618
OpenAlex:	W4394726437
publication_identifier.sciact_skif_identifier_type:	606

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