Tris(trifluoromethyl)germanium iodide as a new cross-linking agent in the synthesis of clathrochelates: monomeric mono- and binuclear iron(II) complexes formed by capping with germanium(IV)

Voloshin, Yan Z.; Varzatskii, Оleg А.; Strizhakova, Nataly G.; Tkachenko, E. Yu.

doi:10.1016/s0020-1693(99)00472-7

Cited by 18 publications

(8 citation statements)

References 26 publications

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“…No signal of the carbon atom co valently linked to the boron atom is observed because of its high quadrupole moment. The characteristics of the UV-Vis spectra of acetoni trile solutions of the initial ferrocenylboronic acid, the [1](BF 4 ) and [4](BF 4 ) complexes, and their clathrochelate [Fe(DXO) 3 (HCOEt) 3 (BBu)](BF 4 ) analog ( [5](BF 4 )) with the alkylboronate cross linking fragment 11 are list ed in Table 1. The bands with maxima at ~200 nm in the spectra of ferrocenylboronic acid and its derivatives are assigned 12 to the Lπ → Md charge transfer in the ferroce nyl substituents.…”

Section: Resultsmentioning

confidence: 99%

“…The maxima in the range from 220 to 280 nm are superposition of the π-π* transition bands in the clathrochelate framework and the forbidden Lπ → Md charge transfer bands (CTBs) in the ferrocenyl fragments. This causes an increase in their molar absorption coeffi cients as compared with the spectra of ferrocenylbo ronic acid and the aliphatic [5](BF 4 ) clathrochelate. The UV-Vis spectra of the complexes synthesized in the vis ible region are determined by the Fe en d → L macro π* charge transfer in the clathrochelate framework from the encap sulated iron(II) ion to the macrobicyclic ligand.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9] In particular, the synthesis of the iron(II) and cobalt(II) semiclathroche lates with the apical ferrocenyl substituents has earlier been reported. The following condensation of these semi сlathrochelates with an aqueous solution of formalde hyde afforded the clathrochelates with 1,3,5 triazacyclo hexane ring as an apical substituent.…”

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Synthesis and structure of the ferrocenylboron-capped clathrochelate iron(ii) oximehydrazonates

et al. 2008

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The direct template macrocyclization of 2,3 butanedione monooxime hydrazone (HDXO) with ferrocenylboronic acid on the iron(II) ion matrix afforded the ferrocenylboron capped semi clathrochelate iron(II) oximehydrazonate. The H + ion catalyzed macrocyclization of this precursor with an excess of triethyl orthoformate gave the clathrochelate complex with syn,syn,syn orientation of the ethoxy substituents relative to the 1,3,5 triazacyclohexane ring. The complexes synthesized were characterized using elemental analysis, IR and UV-Vis spectroscopies, MALDI TOF mass spectrometry, 1 H and 13 C{ 1 H} NMR, 57 Fe Mössbauer spectroscopies, and X ray diffraction analysis.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Synthesis and structure of the ferrocenylboron-capped clathrochelate iron(ii) oximehydrazonates

et al. 2008

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“…A number of the macrobicyclic iron and cobalt tris-dioximates (clathrochelates) formed by capping with Lewis-acidic derivatives of the p-elements of III, IV and V Periods have been isolated and structurally characterized up to date [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Most of them have been synthesized using the direct template reactions on the corresponding metal ion as a matrix, and their molecules with the equivalent chelate and capping fragments have one C 3 axis (passing through the two capping atoms) and three C 2 axes (passing through the middles of the C-C bonds in α-dioximate chelate fragments).…”

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New types of the germanium-capped clathrochelate iron(II) and cobalt(III) tris-dioximates: The synthesis, structure and electrochemical properties

Voloshin

Korobko

Dolganov

et al. 2011

Inorganic Chemistry Communications

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“…Crystallographic data, X ray diffraction experiment details, and structure refinement parameters for 4•[FeCl4 -] and 6•0.75CHCl3 …”

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Macrocyclization of the semiclathrochelate o-carboranylboronate and n-butylboronate iron(II) oximehydrazonates: synthesis and structure of clathrochelate products and unexpected allosteric effect of the apical substituent

et al. 2007

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The template condensation of diacetylmonooxime hydrazone (HDXO) with n butylboronic acid and dimethyl ester of o carboranyldiboronic acid on the iron(II) ion matrix afforded the [Fe(DXO) 3 (ВBu)](BF 4 ) and [Fe(DXO) 3 (Вo carb)](BF 4 ) semiclathrochelates. The Н + ion catalyzed macrocyclization of these precursors with an excess of formaldehyde and triethyl orthoformate (TOF) resulted in the corresponding macrobicyclic complexes. In the case of o carboranylboronate semiclathrochelate, the macrocyclization with TOF gave the clathro chelate with the previously unknown syn,syn,anti orientation of the ethoxy substituents rela tive to the 1,3,5 triazacyclohexane capping fragment. The complexes obtained were character ized using elemental analysis, IR, UV Vis, MALDI TOF mass, 1 H, 11 B, and 13 C NMR, and 57 Fe Mössbauer spectroscopies and X ray crystallography.A number of mono and binuclear semiclathrochelate iron(II) and cobalt(II,III) tris oxime hydrazonates with bo ron , tin , antimony, and germanium containing cross linking apical groups have been obtained up to date; their Н + catalyzed condensation with triethyl orthoformate (TOF) gave in each case a sole isomer of the clathrochelate complex. In the case of boron containing clathrochelates, the ethoxy groups and the semiclathrochelate fragment are syn,syn,syn oriented with respect to the mean plane of the 1,3,5 triazacyclohexane ring, 1 whereas in the tin , antimony , and germanium containing complexes, the ethoxy groups have the anti,anti,anti orientation. 2-4 This difference was explained 5 by the change in the geometry of the semiclathrochelate precursor from trigonal pris matic (TP) for boron containing compounds to trigonal antiprismatic (TAP) for other types of cross linking groups.In this study, we planned to synthesize the binuclear clathrochelate oximehydrazonates using an о carboranyl diboronic acid derivative and to obtain previously un known n butylboronate iron(II) semiclathrochelate and to perform its macrocyclization with TOF. Results and DiscussionOnly few о carborane containing organoboron com pounds with the С-B bond, obtained by reactions of boron trichloride with appropriate С lithium derivatives, are described in the literature. 6 We synthesized methyl ester of о carboranyldiboronic acid (1) by a similar pro cedure starting from о carborane with chlorodimethoxy borane as a borylating agent (Scheme 1). According to 11 B{ 1 H} NMR spectrum of the reaction mixture, the de gree of conversion was ~75%. Apart from signals of the boron atoms of the symmetrically substituted carborane polyhedron, this spectrum contained the characteristic * Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.

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Tris(trifluoromethyl)germanium iodide as a new cross-linking agent in the synthesis of clathrochelates: monomeric mono- and binuclear iron(II) complexes formed by capping with germanium(IV)

Cited by 18 publications

References 26 publications

Synthesis and structure of the ferrocenylboron-capped clathrochelate iron(ii) oximehydrazonates

Synthesis and structure of the ferrocenylboron-capped clathrochelate iron(ii) oximehydrazonates

New types of the germanium-capped clathrochelate iron(II) and cobalt(III) tris-dioximates: The synthesis, structure and electrochemical properties

Macrocyclization of the semiclathrochelate o-carboranylboronate and n-butylboronate iron(II) oximehydrazonates: synthesis and structure of clathrochelate products and unexpected allosteric effect of the apical substituent

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