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Voloshin, Yan Z.; Polshin, Ernest V.; Nazarenko, Alexander Y.

doi:10.1023/a:1021215817257

Cited by 31 publications

(19 citation statements)

References 21 publications

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“…We assigned, doublet Mössbauer parameters of the iron atom of the ferrocenyl fragment and its spatial and electronic structure remain unchanged upon the macrocyclization. An increase in the QS value for the central iron(II) ion upon macrocycliza tion causes an approach of its geometry to trigonal pris matic, 16 which is in agreement with the X ray diffraction data (see Table 2). An increase in the IS value on going from the semiclathrochelate complex to its macrobi cyclic derivative indicates an increase in the s electron density on the nucleus of the central iron(II) ion and, hence, an increase in the ligand field strength upon macro cyclization.…”

Section: Resultssupporting

confidence: 81%

“…According to the X ray diffraction data, all the three ethoxy substituents have the same orientation relative to the plane passing through the nitrogen atoms of the 1,3,5 triazacyclohexane ring as the semiclathro chelate fragment (syn,syn,syn orientation). Correspond ingly, the hydrogen atoms at С(13), С (16), and С (19) atoms have the anti,anti,anti orientation relative to the semiclathrochelate fragment.…”

Section: Resultsmentioning

confidence: 99%

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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: Resultssupporting

confidence: 81%

Section: Resultsmentioning

confidence: 99%

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

et al. 2008

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“…The TP-TAP geometry of the low spin iron(II) com plexes can be deduced with high accuracy using the QS and the partial quadrupole splitting (PQS) values 14, 15 :…”

Section: Resultsmentioning

confidence: 99%

Template synthesis and structures of bis-ferrocenylboronate macrobicyclic iron(ii) tris-dioximates

et al. 2008

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A series of ferrocenylboron capped tris dioximate iron(II) clathrochelates was synthesized by the template condensation of three molecules of dimethylglyoxime (H 2 Dm), cyclohexanedione 1,2 dioxime (H 2 Nx), or cyclooctanedione 1,2 dioxime (H 2 Ox) and two molecules of ferrocenylbo ronic acid (FcB(OH) 2 ) on the Fe 2+ ion matrix. The yields of the clathrochelate derivatives of alicyclic dioximes were substantially higher than that of their acyclic analog, because the molecules of alicyclic H 2 Nx and H 2 Ox α dioximes have the s cis configuration suitable for complex formation, whereas the H 2 Dm molecules in solution have the s trans configuration. The synthesized compounds were characterized using elemental analysis, IR and UV-Vis spectroscopies, MALDI TOF mass spec trometry, 1 H and 13 C{ 1 H} NMR and 57 Fe Mössbauer spectroscopies, and X ray diffraction analysis. The crystal of FeDm 3 (BFc) 2 •CHCl 3 contains two types of crystallographically nonequivalent clathrochelate molecules. The intermolecular contacts C-H...Cp formed by the ferrocenyl frag ments and cyclooctane carbocycles and the interactions Cp-H...O were observed in the crystal of FeOx 3 (BFc) 2 . The structural lability of the cyclooctane substituents allows the FeOx 3 (BFc) 2 mole cules to arrange by the "bump into hollow" mode because of attractive H...H interactions between the ribbed substituents of the neighboring molecules. The geometry of the ferrocenylborate iron(II) clathrochelates is intermediate between a trigonal prism and a trigonal antiprism.Among a variety of the multicentered hybrid and poly nuclear d metal complexes, the polytopic complexes with ferrocenyl fragments able to undergo reversible redox processes at relatively low potentials are worth of special attention. Earlier, both the ferrocenylboron capped iron(II) and cobalt(II, III) oximehydrazonate clathroche lates and semiclathrochelates 1-3 and some α dioximate iron(II) complexes with apical ferrocenyl substituents 4 have been synthesized.During the last years, the ferrocene derivatives are used successfully for controlling the complex radical polymerization of vinyl monomers. 5,6 Therefore, we in tended to obtain the iron(II) clathrochelates with two apical ferrocenyl substituents and then to study the influ ence of these complexes on polymerization processes. The synthetic and structural results of this study are dis cussed in the present paper. ExperimentalCommercial dimethylglyoxime, cyclohexanedione 1,2 dioxime (nioxime), FeCl 2 •4H 2 O (Fluka), and ferrocenylboronic acid FcB(OH) 2 (Aldrich) were used. Cyclooctanedione 1,2 dioxime (octoxime) was synthesized as described earlier. 7 * Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry.

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“…The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, 57 Fe Mössbauer (for the X-rayed iron complexes), 1 H, 11 B, 13 C and 19 F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry (CV) and gas chromatography (GC).…”

Section: Synthesismentioning

confidence: 99%

Molecular design of cage iron(ii) and cobalt(ii,iii) complexes with a second fluorine-enriched superhydrophobic shell

et al. 2015

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Pentafluorophenylboron-capped iron and cobalt(II) hexachloroclathrochelate precursors were obtained by the one-pot template condensation of dichloroglyoxime with pentafluorophenylboronic acid on iron and cobalt(II) ions under vigorous reaction conditions in trifluoroacetic acid media. These reactive precursors easily undergo nucleophilic substitution with (per)fluoroarylthiolate anions, giving (per)fluoroarylsulfide macrobicyclic complexes with encapsulated iron and cobalt(II) ions; nucleophilic substitution of the cobalt(II) hexachloroclathrochelate precursor with a pentafluorophenylsulfide anion gave the target hexasulfide monoclathrochelate and the mixed-valence Co(III)Co(II)Co(III) bis-clathrochelate as a side product. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (57)Fe Mössbauer (for the X-rayed iron complexes), (1)H, (11)B, (13)C and (19)F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry and gas chromatography. As can be seen from the single-crystal X-ray diffraction data, the second superhydrophobic shell of such caged metal ions is formed by fluorine atoms of both the apical and ribbed (per)fluoroaryl peripheral groups. The main bond distances and chelate N=C-C=N angles in their molecules are similar, but rotational elongation (contraction) along the molecular C3-pseudoaxes, accompanied by changes in the geometry of the corresponding MN6-coordination polyhedra from a trigonal prism to a trigonal antiprism, allowed encapsulating Fe(2+), Co(2+) and Co(3+) ions. The nature of an encapsulated metal ion and its oxidation state affect the M-N bond lengths, and, for cobalt(ii) clathrochelate with an electronic configuration d(7) the Jahn-Teller structural effect is observed as an alternation of the Co-N distances. Pentafluorophenylboron-capped hexachloroclathrochelate precursors, giving stable catalytically active metal(I)-containing intermediates due to the electron-withdrawing effect of their six ribbed chlorine substituents, were found to show moderate electrocatalytic activity in a 2H(+)/H2 hydrogen-forming reaction. In the case of their ribbed-functionalized sulfide derivatives, the strong electron-withdrawing (per)fluoroaryl groups do not stabilize the reduced electrocatalytically active metal(i)-containing species as their mesomeric effect is absent or substantially decreased by steric hindrances between them.

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Cited by 31 publications

References 21 publications

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

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

Template synthesis and structures of bis-ferrocenylboronate macrobicyclic iron(ii) tris-dioximates

Molecular design of cage iron(ii) and cobalt(ii,iii) complexes with a second fluorine-enriched superhydrophobic shell

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