Formation of the second superhydrophobic shell around an encapsulated metal ion: synthesis, X-ray structure and electrochemical study of the clathrochelate and bis-clathrochelate iron(II) and cobalt(II, III) dioximates with ribbed perfluoroarylsulfide substituents

Formation of the second superhydrophobic shell around an encapsulated metal ion: synthesis, X-ray structure and electrochemical study of the clathrochelate and bis-clathrochelate iron(II) and cobalt(II, III) dioximates with ribbed perfluoroarylsulfide substituents Full article

Journal

Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234

Output data

Year: 2012, Volume: 41, Number: 3, Pages: 737-746 Pages count : DOI: 10.1039/c1dt10500k

Authors

Voloshin Y. Z. ¹ , Belaya (Makarenko) I. G. ¹ , Belov A. S. ¹ , Platonov V. E. ² , Maksimov A. M. ² , Vologzhanina A. V. ¹ , Starikova Z. A. ¹ , Dolganov A. V. ¹ , Novikov V. V. ¹ , Bubnov Y. N. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, AN Nesmeyanov Organoelement Cpds Inst, Moscow 119991, Russia
2	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia

The nucleophilic substitution of six chlorine atoms of the n-butylboron-capped clathrochelate iron and cobalt(II) precursors with perfluoroarylthiolate anions afforded the hexaperfluoroarylsulfide macrobicyclic iron and cobalt(II) tris-dioximates. The complexes obtained are soluble in aromatic and aliphatic hydrocarbons as well as in polar aprotonic solvents due to the presence of the superhydrophobic fluorine-containing molecular periphery. As it follows from the X-ray data for five iron and cobalt mono- and bis-clathrochelates, the geometry of their macrobicyclic frameworks is affected by both the nature of an encapsulated metal ion and that of the ribbed substituents. Bis-capping fragment (CoO6)-O-II of the (CoCoCoIII)-Co-III-Co-II bis-clathrochelate possesses a trigonal antiprismatic geometry, all the (CoN6)-N-II coordination polyhedra are trigonal-prismatic, and those of the encapsulated iron(II) and cobalt(III) ions are intermediate between them. The wide range of Co-N distances as well as the significant shifts of the encapsulated cobalt(II) ions from the centres of their N-6-coordination polyhedra were explained by the Jahn-Teller distortion. The EPR and magnetometry data are also characteristic of the low-spin cobalt(II) complexes with this distortion. The parameters of the Fe-57 Mossbauer spectra of the iron macrobicycles are characteristic of the low-spin iron(II) complexes. The cyclic voltammograms (CVs) for the complexes studied contain the one-electron oxidation and reduction waves assigned to metal-centered redox-processes. The Fe2+/3+ and Co2+/3+ oxidations are quasi-reversible or irreversible. The anionic clathrochelate species resulting from the reversible Co2+/+ reductions are stable on the CV time scale, whereas their iron(I)-containing analogs are unstable.

Voloshin Y.Z. , Belaya (Makarenko) I.G. , Belov A.S. , Platonov V.E. , Maksimov A.M. , Vologzhanina A.V. , Starikova Z.A. , Dolganov A.V. , Novikov V.V. , Bubnov Y.N.
Formation of the second superhydrophobic shell around an encapsulated metal ion: synthesis, X-ray structure and electrochemical study of the clathrochelate and bis-clathrochelate iron(II) and cobalt(II, III) dioximates with ribbed perfluoroarylsulfide substituents
Dalton Transactions. 2012. V.41. N3. P.737-746. DOI: 10.1039/c1dt10500k WOS Scopus РИНЦ OpenAlex

Web of science:	WOS:000298753800007
Scopus:	2-s2.0-84555196190
Elibrary:	17970777
OpenAlex:	W2040623099

DB	Citing
Web of science	41
Scopus	41
Elibrary	39
OpenAlex	41