Reversible Binding of Dioxygen by a Non‐Transition‐Metal Complex

Абакумов, Г. А.; Poddel’sky, Andrey I.; Grunova, Ekaterina; Cherkasov, V. K.; Fukin, Georgy K.; Kurskii, Yury A.; Abakumova, L. G.

doi:10.1002/ange.200462503

Cited by 22 publications

(22 citation statements)

References 25 publications

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“…In main-group-metal chemistry the only example of a cycloaddition with reversible binding of dioxygen was found to be mediated by triphenylstibiumcatecholate and -amidophenolate complexes. [14] Note that the reactions of [(dpp-bian)MgA C H T U N G T R E N N U N G (thf) 3 ] with R À X (Scheme 1) also proceed by addition across the metal-ligand 1,3-dipole and result in new carbon-carbon and magnesium-halide bonds. [15] In the context of activation of carbon-carbon multiple bonds in main-group-metal complexes, the recently reported addition of H 2 C=CH 2 to the metal-metal triple bond in ArSnSnAr is remarkable.…”

Section: Resultsmentioning

confidence: 97%

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Fedushkin¹,

Nikipelov²,

Morozov³

et al. 2011

Chemistry A European J

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103

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Acetylene, phenylacetylene, and alkylbutynoates add reversibly to (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene) to give addition products [dpp-bian(R(1)C=CR(2))]Ga-Ga[(R(2)C=CR(1))dpp-bian]. The alkyne adds across the Ga-N-C section, which results in new carbon-carbon and carbon-gallium bonds. The adducts were characterized by electron absorption, IR, and (1)H NMR spectroscopy and their molecular structures have been determined by single-crystal X-ray analysis. According to the X-ray data, a change in the coordination number of gallium from three [in (dpp-bian)Ga-Ga(dpp-bian)] to four (in the adducts) results in elongation of the metal-metal bond by approximately 0.13 Å. The adducts undergo a facile alkynes elimination at elevated temperatures. The equilibrium between [dpp-bian(PhC=CH)]Ga-Ga[(HC=CPh)dpp-bian] and [(dpp-bian)Ga-Ga(dpp-bian) + 2 PhC≡CH] in toluene solution was studied by (1)H NMR spectroscopy. The equilibrium constants at various temperatures (298≤T≤323 K) were determined, from which the thermodynamic parameters for the phenylacetylene elimination were calculated (ΔG°=2.4 kJ mol(-1), ΔH°=46.0 kJ mol(-1), ΔS°=146.0 J K(-1) mol(-1)). The reactivity of (dpp-bian)Ga-Ga(dpp-bian) towards alkynes permits use as a catalyst for carbon-nitrogen and carbon-carbon bond-forming reactions. The bisgallium complex was found to be a highly effective catalyst for the hydroamination of phenylacetylene with anilines. For instance, with [(dpp-bian)Ga-Ga(dpp-bian)] (2 mol%) in benzene more than 99% conversion of PhNH(2) and PhC≡CH into PhN=C(Ph)CH(3) was achieved in 16 h at 90 °C. Under similar conditions, the reaction of 1-aminoanthracene with PhC≡CH catalyzed by (dpp-bian)Ga-Ga(dpp-bian) formed a carbon-carbon bond to afford 1-amino-2-(1-phenylvinyl)anthracene in 99% yield.

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Section: Resultsmentioning

confidence: 97%

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Fedushkin¹,

Nikipelov²,

Morozov³

et al. 2011

Chemistry A European J

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103

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“…(2) proves this transfer of an electron from the dpp-BIAN ligand in 1 to the organic reactant according to the change in the oxidation state of the dpp-BIAN ligand from the di-to the mono-anion and the reduction of the peroxide to benzoate anions (Scheme 5). The dimeric complex 2 is sensitive against moisture and air, is only poorly soluble in diethyl ether, but moderately soluble in benzene and toluene, and melts at 157 • C without decomposition.…”

Section: Introductionmentioning

confidence: 78%

“…Metal complexes with ligands which are able to adopt different valence states like 1,2-diimines, ketimines, and semiquinones (SQ) show quite specific properties, as for instance the reversible intramolecular metal-to-ligand electron transfer in transition metal complexes of o-benzosemiquinones (SQ) [1] or the reversible uptake of oxygen by triphenylantimony amidophenolate affording the endoperoxide (Scheme 1) [2].…”

Section: Introductionmentioning

confidence: 99%

Electron Release and Proton Acceptance Reactions of (dpp-BIAN)Mg(THF)₃

Fedushkin

Chudakova

Hummert

et al. 2008

Zeitschrift Für Naturforschung B

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(dpp-BIAN)Mg(THF) 3 (1) (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) and (PhCOO) 2 react with splitting of the peroxide bridge and formation of the dimeric magnesium benzoate [(dpp-BIAN)MgOCOPh(THF)] 2 (2). The reaction of 1 with PhCOOH yields the dimeric magnesium benzoate [(dpp-BIAN)(H)MgOCOPh(THF)] 2 (3), whereas 1 and furanyl-2-carboxylic acid react with liberation of hydrogen and formation of (dpp-BIAN)Mg[OCO(2-C 4 H 3 O)] 2 Mg(dpp-BIAN)(THF) (4). Compounds 2, 3, and 4 have been characterized by elemental analysis, IR spectroscopy, and X-ray structure analysis, compound 3 also by 1 H NMR spectroscopy. The eightmembered metallacycles of the centrosymmetric dimers 2 and 3 are almost completely planar. The two magnesium atoms in 4 show different coordination spheres; one is surrounded by its ligands in a trigonal bipyramidal manner, the other one in a tetrahedral fashion. The Mg··· Mg separations in 2, 3 and 4 are 4.236, 4.296, and 4.030Å, respectively.

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“…The higher antioxidant activity defines the probability of interaction with active radicals and molecular oxygen. The reactivity of complexes 2e5 is connected with a fixation of molecular oxygen via the stage of complex oxidation to cationic form and formation of superoxide radical-anion finally yielding spiroendoperoxide containing peroxo-fragment [27,29,31].…”

Section: Discussionmentioning

confidence: 99%

Radical scavenging activity of sterically hindered catecholate and o-amidophenolate complexes of LSbVPh3 type

Smolyaninov

Antonova

Poddel’sky

et al. 2011

Journal of Organometallic Chemistry

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Reversible Binding of Dioxygen by a Non‐Transition‐Metal Complex

Cited by 22 publications

References 25 publications

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Electron Release and Proton Acceptance Reactions of (dpp-BIAN)Mg(THF)₃

Radical scavenging activity of sterically hindered catecholate and o-amidophenolate complexes of LSbVPh3 type

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Reversible Binding of Dioxygen by a Non‐Transition‐Metal Complex

Cited by 22 publications

References 25 publications

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Electron Release and Proton Acceptance Reactions of (dpp-BIAN)Mg(THF)3

Radical scavenging activity of sterically hindered catecholate and o-amidophenolate complexes of LSbVPh3 type

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Electron Release and Proton Acceptance Reactions of (dpp-BIAN)Mg(THF)₃