Unexpected reactivity of an alkylaluminum complex of a non-innocent 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian)

Moskalev, M. V.; Lukoyanov, Anton N.; Баранов, Е. В.; Fedushkin, Igor L.

doi:10.1039/c6dt01750a

Cited by 19 publications

(11 citation statements)

References 54 publications

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“…One can conclude that the rigid dpp-Bian ligand serves well for stabilization of the Al−C bond. Such a behavior was recently reported 104. These led to reduction of the cationic activator [Ph 3 C][B(C 6 F 5 ) 4 ] instead of Al−C bond cleavage.…”

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confidence: 57%

Synthesis and ε-Caprolactone Polymerization Activity of Electron-Deficient Gallium and Aluminum Species Containing a Charged Redox-Active dpp-Bian Ligand

et al. 2019

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The synthesis of electron-deficient gallium- and aluminum-centered species containing a redox-active dpp-Bian ligand (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) is described. The reaction of digallane [(dpp-Bian)Ga–Ga(dpp-Bian)] with [Ph3C][PF6] or AgPF6 resulted in polyoxidized species [(dpp-Bian)GaF2]2 (1), [(dpp-Bian)H2][PF6] (2), and [(dpp-Bian)GaF(O2PF2)]2 (3). The reaction of digallane with B(C6F5)3 led to electron-deficient gallylene [(dpp-Bian)GaB(C6F5)3] 4 of a dpp-Bian radical anion. The soft oxidation of digallane with tosyl cyanide gave the trinuclear cationic species [(dpp-Bian)Ga(Tos)3Ga(Tos)3Ga(dpp-Bian)][Ga(CN)4] (5) containing dpp-Bian radical anions. The reaction of [(dpp-Bian)AlEt2] with 1 equiv of [Ph3C][B(C6F5)4] resulted in the cationic complex [(dpp-Bian)AlEt2][B(C6F5)4] (6) of neutral dpp-Bian, while the treatment of [(dpp-Bian)AlEt(Et2O)] with 1 equiv of [Ph3C][B(C6F5)4] resulted in the compound [(dpp-Bian)AlEt(Et2O)][B(C6F5)4] (7) of a dpp-Bian radical anion. The reaction of diethylaluminum derivative [(dpp-Bian)AlEt2] with 1 equiv of B(C6F5)3 gave the cationic complex [{(dpp-Bian)AlEt}2F][EtB(C6F5)3] (8) containing radical-anion dpp-Bian ligands. The paramagnetic compounds 1, 2, 4, 5, 7, and 8 were characterized by electron paramagnetic resonance spectroscopy, and the diamagnetic complex 6 was characterized by NMR spectroscopy. The molecular structures of 1–6 and 8 were established by single-crystal X-ray diffraction analysis. Compounds 4 and 6–8 were found to be active initiators for immortal ring-opening polymerization of ε-caprolactone.

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confidence: 57%

Synthesis and ε-Caprolactone Polymerization Activity of Electron-Deficient Gallium and Aluminum Species Containing a Charged Redox-Active dpp-Bian Ligand

et al. 2019

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“…10 The Berben group observed aluminum-ligand cooperative addition of phenol, benzyl alcohols, 13 water, 14 and formic acid 15 to their bis(iminopyridine)-ligated aluminum hydride. 16 Other examples of aluminum-based cooperative OHaddition reactions were provided by Fedushkin 17 and recently by Zhu. 18 The formal oxidative addition of ROH to phosphorus(III), likely assisted by ELC, was reported for structurally constrained systems by Goicoechea 19 and Dobrovetsky.…”

Section: Introductionmentioning

confidence: 99%

Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

Sigmund

Greb

2020

Chem. Sci.

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“…Recently, we have shown that in alkylaluminum complexes, the dpp-Bian is acting rather as stabilizing ligand toward alkyl–aluminum bond. For instance, Ph 2 CO and PhCCH do not insert into the Al–C(Et) bond in compound (dpp-Bian 2– )AlEt(Et 2 O): the ketone replaces the coordinating solvent, while the alkyne forms the cycloadduct through the formation of C–C and C–Al bonds . The situation seems to be similar to gallium hydrides 1 and 4 .…”

Section: Discussionmentioning

confidence: 93%

Gallium Hydrides with a Radical-Anionic Ligand

et al. 2017

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The reaction of ClGaH with a sodium salt of the dpp-Bian radical-anion (dpp-Bian)Na (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords paramagnetic gallane (dpp-Bian)Ga(Cl)H (1). Oxidation of (dpp-Bian)Ga-Ga(dpp-Bian) (2) with NO results in the dimeric oxide (dpp-Bian)Ga(μ-O)Ga(dpp-Bian) (3). A treatment of the oxide 3 with phenylsilane affords paramagnetic gallium hydrides (dpp-Bian)GaH (4) and (dpp-Bian)Ga{OSi(Ph)H}H (5) depending on the reagent's stoichiometry. The reaction of digallane 2 with benzaldehyde produces pinacolate (dpp-Bian)Ga(OCHPh) (6). In the presence of PhSiH, the reaction between digallane 2 and benzaldehyde (2: PhSiH: PhC(H)O = 1:4:4) affords compound 4. The newly prepared complexes 1, 3-6 consist of a spin-labeled diimine ligand-dpp-Bian radical-anion. The presence of the ligand-localized unpaired electron allows the use of the ESR spectroscopy for characterization of the gallium hydrides reported. The molecular structures of compounds 1, 3-6 have been determined by the single-crystal X-ray analysis.

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Unexpected reactivity of an alkylaluminum complex of a non-innocent 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian)

Cited by 19 publications

References 54 publications

Synthesis and ε-Caprolactone Polymerization Activity of Electron-Deficient Gallium and Aluminum Species Containing a Charged Redox-Active dpp-Bian Ligand

Synthesis and ε-Caprolactone Polymerization Activity of Electron-Deficient Gallium and Aluminum Species Containing a Charged Redox-Active dpp-Bian Ligand

Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

Gallium Hydrides with a Radical-Anionic Ligand

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