Pathways of Directed Synthesis of Iron(II) Clathrochelates and Polyclathrochelates with Non-Equivalent Capping Groups Starting from Antimony- and Germanium-Containing Precursors Full article
Journal |
Inorganica Chimica Acta
ISSN: 0020-1693 , E-ISSN: 1873-3255 |
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Output data | Year: 2004, Volume: 357, Number: 11, Pages: 3187-3204 Pages count : 18 DOI: 10.1016/j.ica.2004.03.050 | ||||||||
Tags | 57Fe Mössbauer spectra, Cage compounds, Clathrochelate complexes, Crystal structure, EXAFS | ||||||||
Authors |
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Affiliations |
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Funding (1)
1 | Russian Foundation for Basic Research | 03-03-32531 |
Abstract:
Alternative methods for directed syntheses of clathrochelates and polyclathrochelates with two non-equivalent capping fragments using semiclathrochelate precursors and capping group reactions are described. The lability of antimony-capped iron(II) clathrochelates in remetallation (a capping group exchange) reactions allowed to obtain of mono- and bis-clathrochelates of a general formula FeNx3X1X2 and (FeNx3X1)2X2 (where Nx2− is cyclohexanedione-1,2-dioxime dianion; X1, X2 are different capping groups). The first and unique dioximate [Fe(HNx)3(Sb(C6H5)3)](ClO4) semiclathrochelate was isolated and characterized. The reaction of this complex with differing mono- and bifunctional cross-linking agents (Lewis acids) led to the formation of clathrochelates molecules with non-equivalent capping groups. The clathrochelates with a labile triethylantimony capping group underwent remetallation in the presence of silicon dioxide as a catalyst. The first stage led to the formation of a surface-immobilized mixed SbSi-capped clathrochelate, which under the action of another capping agent desorbed from the surface gives a mono- or bis-clathrochelate depending on the nature of this agent. An alternative pathway using the bis-capping agents has been implemented for synthesis of bis-clathrochelates when reactive fragments of an initial azomethine ligand demonstrate essentially different chemical properties. The oximehydrazonate germanium-capped iron(II) bis-clathrochelate was synthesized starting from a bis-semiclathrochelate, which was initially isolated with bis-capping germanium(IV) tetraethoxide. A further H+-catalyzed macrocyclization with triethyl orthoformate produced germanium-capped bis-clathrochelate. The obtained mono- and bis-clathrochelates have been characterized using elemental analysis, PD mass, IR, UV–Vis and 1H and 13C NMR spectra, and X-ray crystallography (for FeNx3(Sb(C2H5)3)2 complex), as well as by cyclic voltammograms. The distortion angle ϕ values and the main distances in the clathrochelate frameworks have been deduced using 57Fe Mössbauer parameters, and EXAFS data and molecular mechanics calculations, respectively.
Cite:
Voloshin Y.Z.
, Varzatskii O.A.
, Korobko S.V.
, Antipin M.Y.
, Vorontsov I.I.
, Lyssenko K.A.
, Kochubey D.I.
, Nikitenko S.G.
, Strizhakova N.G.
Pathways of Directed Synthesis of Iron(II) Clathrochelates and Polyclathrochelates with Non-Equivalent Capping Groups Starting from Antimony- and Germanium-Containing Precursors
Inorganica Chimica Acta. 2004. V.357. N11. P.3187-3204. DOI: 10.1016/j.ica.2004.03.050 WOS Scopus РИНЦ
Pathways of Directed Synthesis of Iron(II) Clathrochelates and Polyclathrochelates with Non-Equivalent Capping Groups Starting from Antimony- and Germanium-Containing Precursors
Inorganica Chimica Acta. 2004. V.357. N11. P.3187-3204. DOI: 10.1016/j.ica.2004.03.050 WOS Scopus РИНЦ
Dates:
Submitted: | Nov 17, 2003 |
Accepted: | Mar 5, 2004 |
Published online: | Jul 3, 2004 |
Published print: | Aug 1, 2004 |
Identifiers:
Web of science | WOS:000223311700009 |
Scopus | 2-s2.0-3242791014 |
Elibrary | 13471453 |
Chemical Abstracts | 2004:594567 |
Chemical Abstracts (print) | 141:296129 |
OpenAlex | W1965730525 |