The Synthesis and Characterization of Mononuclear and Binuclear Iron(II) Clathrochelate Complexes Derived from 2,3-Butanedione Oxime Hydrazone

Belinski, Judy A.; Squires, Marjorie E.; Kuchna, John M.; Bennett, Bruce; Grzybowski, Joseph J.

doi:10.1080/00958972.1988.9728152

Cited by 16 publications

(25 citation statements)

References 8 publications

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“…According to the 1 H and 13 C{ 1 H} NMR data, the reaction gave a mixture of the complexes, which contains almost no target [4](BF 4 ) clathrochelate. The reflux of the reaction mixture afford ed the complete dissolution of the [1](BF 4 ) precursor, but the analysis of the 1 H and 13 C{ 1 H} NMR spectra of the products showed that a mixture of the macrocyclic and open chain compounds, which contains almost no target complex, was formed in this case. These attempts were unsuccessful because of both the absence of an sufficient amount of the H + ions for the complete macrocyclization reaction and the oxidation of ferrocenyl fragments of the [1](BF 4 ) and [4](BF 4 ) complexes by admixture of atmo spheric oxygen at high temperatures.…”

Section: Resultsmentioning

confidence: 88%

“…In the first case, the iron(II) tris oximehydrazonate [2](BF 4 ) 2 was initially obtained and then, in the second step, under went condensation with ferrocenylboronic acid (Scheme 1). The overall yield of the [1](BF 4 ) semiclathrochelate was 23%. Since the overall yield of the target product via this scheme was low, the template condensation of three molecules of 2,3 butanedione monooxime hydrazone (HDXO) and ferrocenylboronic acid on the iron(II) ion matrix was used in the second procedure.…”

Section: Resultsmentioning

confidence: 99%

“…At first we attempted to obtain [4](BF 4 ) by the condensation of the [1](BF 4 ) complex with TOF in the presence of catalytic amounts of trifluoroacetic anhydride as described earlier 11 for the alkylborate and o carbonylborate oxime hydrazonate iron(II) clathrochelates. The red orange col oration of the reaction mixture has changed to dark red, but only partial dissolution of the initial [1](BF 4 ) semi clathrochelate was observed. According to the 1 H and 13 C{ 1 H} NMR data, the reaction gave a mixture of the complexes, which contains almost no target [4](BF 4 ) clathrochelate.…”

Section: Resultsmentioning

confidence: 99%

“…The ferrocenylboron capped semiclathrochelate [1](BF 4 ) was obtained by two different procedures. In the first case, the iron(II) tris oximehydrazonate [2](BF 4 ) 2 was initially obtained and then, in the second step, under went condensation with ferrocenylboronic acid (Scheme 1).…”

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: 88%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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

et al. 2008

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Circular dichroism spectroscopy and DFT calculations in determining absolute configuration and E/Z isomers of conjugated oximes

Rode

Frelek

2017

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The primary purpose of this work was to demonstrate the suitability of circular dichroism (CD) spectroscopy in stereochemical studies of α,β-unsaturated oximes, with particular emphasis on determination of E and Z geometry of the oxime double bond. As models for this study, O-phenyl and O-triphenylmethyl (trityl) oximes of 4-hydroxy-2-methylcyclopent-2-en-1-one were selected. These model compounds differ in both absolute configuration at C4 carbon atom and E-Z configuration of the oxime double bond. The basic dichroic technique applied was electronic circular dichroism (ECD) assisted by quantum-chemical calculations and vibrational circular dichroism (VCD) for selected cases. Such an approach enabled effective implementation of both goals. Thus, we were able to associate the signs of Cotton effects in the range of 190-240 nm with the absolute configuration at C4 and within 240-300 nm with the E- or Z-geometry of the oxime double bond. Within this work, optical activity of the protecting trityl group was also studied towards formation of the propeller-shaped conformations by using the same combined CD/DFT methodology. As shown, the helical structure of the trityl group has a considerable influence on the ECD spectra. However, the MPM and PMP conformers of the trityl group are in fact almost equally populated in the conformational equilibrium, making it impossible to distinguish them. On the other hand, rotamers of the hydroxyl group at C4 show a decisive impact on the VCD spectra in both phenoxy and trityl oximes.

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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 Synthesis and Characterization of Mononuclear and Binuclear Iron(II) Clathrochelate Complexes Derived from 2,3-Butanedione Oxime Hydrazone

Cited by 16 publications

References 8 publications

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

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

Circular dichroism spectroscopy and DFT calculations in determining absolute configuration and E/Z isomers of conjugated oximes

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

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