Zinc molecular complexes with sterically hindered o-quinone and o-iminoquinone

Abakumov, G. A.; Cherkasov, V. K.; Piskunov, A. V.; Meshcheryakova, I. N.; Maleeva, A. V.; Poddel’skii, A. I.; Fukin, Georgy K.

doi:10.1134/s0012500809070064

Cited by 23 publications

(30 citation statements)

References 5 publications

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“…Chloroform-d and pyridine-d 5 were purchased from Cambridge Isotope Laboratories, dried with molecular sieves, and degassed by three freeze−pump−thaw cycles. 4,6-Di-tert-butyl-2-[(2,6-diisopropylphenyl)imino]quinone ( dipp iq), 23 potassium graphite (KC 8 ), 26 uranyl dichloride ([UO 2 Cl 2 (THF) 2 ] 2 ), 27 uranyl triflate UO 2 (OTf) 2 (THF) 3 , 28 and uranium tetrachloride (UCl 4 ) 29 were prepared according to literature procedures. 18-Crown-6 (18-C-6) and B-chlorocatecholborane (Cl-BCat) were purchased from Sigma-Aldrich and dried under vacuum on a Schlenk line overnight prior to use.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…We hypothesized that U–O uranyl bonds could undergo such a conversion with electrophilic carbon-containing substrates when mediated by reduced redox-active ligands. The iminoquinone family would be effective for such a task, as this ligand set has mediated multielectron reactions with low-valent metals − and would obviate the need for an external reductant by its ability to exist in a reduced state (Figure ). The most oxidized form of this ligand, the iminoquinone (iq 0 ), can be reduced to the iminosemiquinone (isq 1– ), which is characterized by a ligand radical.…”

Section: Introductionmentioning

confidence: 99%

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Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

et al. 2018

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A series of uranyl compounds with the redoxactive iminoquinone ligand have been synthesized, and their electronic structures elucidated using multinuclear NMR, EPR, electronic absorption spectroscopies, SQUID magnetometry, and X-ray crystallography. Characterization and analysis of the iminoquinone (iq 0 ) complex, ( dipp iq)UO 2 (OTf) 2 THF (1-iq), the iminosemiquinone (isq 1− ) complex, ( dipp isq) 2 UO 2 THF (2i s q ) , a n d t h e a m i d o p h e n o l a t e ( a p 2 − ) complex, [( dipp ap) 2 UO 2 THF][K(18-crown-6)(THF) 2 ] 2 (3-ap crown) show that reduction events are ligand-based, with the uranium center remaining in the hexavalent state. Reactivity of 2-isq with B-chlorocatecholborane or pivaloyl chloride leads to U−O uranyl bond scission and reduction of U(VI) to U(IV) concomitant with ligand oxidation along with organic byproducts. 18 O isotopic labeling experiments along with IR spectroscopy, mass spectrometry, and multinuclear NMR spectroscopy confirm that the organic byproducts contain oxygen atoms which originate from U−O uranyl bond activation.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

et al. 2018

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“…This interest is due to the redox chemistry of such compounds, which is unusual for the main group elements. 4a-d At the moment a number of non-transition metal complexes with sterically hindered o-iminoquinoid ligands with neutral, 5 radical-anion (o-iminosemiquinolate) 6a-d or dianion (o-amidophenolate) 4a,b,6d,7 forms of the ligand are known. Previously 8 we described the synthesis of indium(III) derivatives based on the neutral or radical-anion (imSQ) form of 4,6-di-tert-butyl-N-(2,6-di-iso-propyl-phenyl)-o-iminobenzoquinone (imQ).…”

Section: Introductionmentioning

confidence: 99%

Indium(iii) complexes with o-iminobenzoquinone in different redox states

et al. 2010

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The indium(III) complexes containing 4,6-di-tert-butyl-N-(2,6-di-iso-propyl-phenyl)o-iminobenzoquinone (imQ) in dianion o-amidophenolate (AP) (1) or radical-anion o-iminobenzosemiquinolate (imSQ) (3) form and iodide ligands (one in the case of 1 or two in the case of 3) have been obtained in the presence of donor agent (tetramethylethylenediamine (TMED)). The 4,6-di-tert-butyl-N-(2,6-di-iso-propyl-phenyl)o-amidophenolate-ethyl-indium(III) (2) was obtained by the exchange reaction of disodium o-amidophenolate (APNa 2 ) with I 2 InEt. Structures of complexes 1, 2 and 3 were determined by X-ray diffraction analysis.Scheme 1 The synthesis of compounds 1 and 2.

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“…The bond lengths C–O and C–N of o ‐iminobenzosemiquinolate fragments of these complexes are typical for o ‐iminobenzosemiquinolate radical‐anion form of ligands (C–O 1.29–1.33 Å, C–N 1.33–1.37 Å) 1c,7. These bonds are considerably shorter than bonds in O, N‐coordinated o ‐amidophenolates (C–O 1.35–1.36 Å, C–N 1.38–1.39 Å) or N‐protonated aminophenolate form (C–O, 1.35–1.36 Å; C–N, 1.42–1.47 Å) but longer than double bonds of o ‐iminobenzoquinones (1.22 Å and 1.29 Å, respectively) 1c,8. In both o ‐iminobenzosemiquinolate parts of organic ligands all C–C distances are not equidistant and demonstrate quinoid‐type alternation.…”

Section: Resultsmentioning

confidence: 99%

The Features of Interaction of Bis(4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐amidophenolato)tin(IV) with Bromine and Iodine

Ilyakina

Poddel’sky

Piskunov

et al. 2012

Zeitschrift anorg allge chemie

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The oxidation of tin(IV) bis-amidophenolate (APiPr) 2 Sn·THF (I) by bromine and iodine leads to the formation of monoradical mixed-ligand complexes (APiPr)(ISQiPr)SnBr·THF (II) and (AP-iPr)(ISQiPr)SnI·THF (III) or diradical complexes (ISQiPr) 2 SnBr 2 (IV) and (ISQiPr) 2 SnI 2 (V), respectively [APiPr = dianion 4,6-di-tert-butyl-depending on the molar ratio of reagents * Prof. Dr. E. V. Ilyakina Fax: +783-4627497 E-Mail: ekaterin_from_nn@bk.ru [a] G.A. Razuvaev 1323(2:1 or 1:1). According to EPR data for compounds II and III, the unpaired electron is delocalized between both organic ligands. The EPR spectrum of IV in toluene matrix at 130 K is typical for diradical species with S = 1 with parameters D = 530 G, E = 105 G. The mixedligand complexes II and III are unstable and undergo to symmetrization leading to formation of IV or V. The molecular structures of IV and V are determined by X-ray analysis.

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Zinc molecular complexes with sterically hindered o-quinone and o-iminoquinone

Cited by 23 publications

References 5 publications

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Uranyl Functionalization Mediated by Redox-Active Ligands: Generation of O–C Bonds via Acylation

Indium(iii) complexes with o-iminobenzoquinone in different redox states

The Features of Interaction of Bis(4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐amidophenolato)tin(IV) with Bromine and Iodine

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