Borane reduction of carbon dioxide bound to diimine-supported aluminum hydrides

Koptseva, Tatyana S.; Moskalev, M. V.; Skatova, Alexandra A.; Bazanov, Andrey A.; Баранов, Е. В.; Rychagova, Elena; Ketkov, S. Yu.; Fedushkin, Igor L.

doi:10.1007/s11172-022-3571-6

Cited by 7 publications

(12 citation statements)

References 29 publications

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“…The calculations were carried out for gas-phase molecules as in our earlier work. 21 We found that in non-polar toluene, the thermodynamic parameters are very close to those obtained in the gas phase (see the Experimental Section).…”

Section: ■ Results and Discussionsupporting

confidence: 71%

“…To reveal the reasons for the different behavior of complex 1 upon interaction with HBpin, HBcat, and BH 3 ·SMe 2 , we performed DFT calculations of the changes in energy accompanying the corresponding processes. The calculations were carried out for gas-phase molecules as in our earlier work . We found that in non-polar toluene, the thermodynamic parameters are very close to those obtained in the gas phase (see the Experimental Section).…”

Section: Resultssupporting

confidence: 56%

“…The τ 4 ′ , value in these complexes varies within a narrow range of 0.88–0.91. Comparison of the Al–O bond lengths in the Al–O–CH 3 fragments demonstrates their slight elongation from 1.699(3) Å in the known complex [{(dpp-bian)Al(OCH 3 )} 2 (μ-O)] to 1.710(5) and 1.738(5) Å in compounds 2 and 4 , respectively. In general, all bond lengths in the coordination sphere of the aluminum atoms in 2 and 4 (Table S2, see the ESI) are in a good agreement with the known four-coordination aluminum complexes. ,, The B–O distances in complex 2 are not equivalent to each other.…”

Section: Resultsmentioning

confidence: 95%

“…In general, all bond lengths in the coordination sphere of the aluminum atoms in 2 and 4 (Table S2, see the ESI) are in a good agreement with the known four-coordination aluminum complexes. 20,21,27 The B−O distances in complex 3) and 1.397(3) Å). 20 In the centrosymmetric dimer 3 (Figure 2), two aluminum atoms are bound by two catecholate ligands: the Al•••Al distance is 3.016(3) Å which excludes a direct metal−metal interaction.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Acenaphthene-1,2-diimine aluminum dihydrides bind CO 2 to form formate, gemdiolate, and carbonate derivatives. Recently, we have carried out the reduction of “captured” CO 2 by BH 3 ·NHMe 2 and HBpin (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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Hydroboration of a Diolate Complex Obtained by Carbon Dioxide Capture with Acenaphthenediimine Aluminum Hydride

et al. 2022

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The reduction of diolate [{(dpp-bian)Al(μ-O2CH2)}2] (1), bearing a redox-active acenaphthene-1,2-diimine ligand (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene), by boranes has been studied. The reaction of 1 with HBpin proceeds with reduction of the C–O bonds in the −O–CH2–O– fragments and results in [{(dpp-bian)Al(OCH3)}(μ-O){Al(OBpin)(dpp-bian)}] (2) and pinBOCH3. The reduction of 1 by HBcat leads to the formation of the compound [{(dpp-bian)Al(μ-Cat)}2] (3) and (CH3OBO)3. BH3·SMe2 reduces diolate 1 to form the complex [{(dpp-bian)Al(OCH3)}(μ-O){Al(OCH2OBH2)(dpp-bian)}] (4). Compounds 2–4 have been characterized by electron paramagnetic resonance and infrared spectroscopy, and their molecular structures have been determined by single-crystal X-ray analysis. Density functional theory calculations have been performed to analyze the reaction energies and a possible mechanism of an initial stage as well as to explain the different product types.

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Section: ■ Results and Discussionsupporting

confidence: 71%

Section: Resultssupporting

confidence: 56%

Section: Resultsmentioning

confidence: 95%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydroboration of a Diolate Complex Obtained by Carbon Dioxide Capture with Acenaphthenediimine Aluminum Hydride

et al. 2022

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Catalytic hydroboration of carbon dioxide and cyclohexyl isocyanate with diimine zinc hydrides

Sokolov,

Skatova,

Moskalev

et al. 2024

Russ Chem Bull

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Reduction of Nitrous Oxide and Binding of Carbon Dioxide by Acenaphthene-1,2-diimine Aluminum Compounds

et al. 2023

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The reaction of dialane [(dpp-bian)Al–Al(dpp-bian)] (1) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with N2O results in the formation of oxide [(dpp-bian)Al(μ2-O)2Al(dpp-bian)] (2). The reaction of the thf adduct of 1, [(dpp-bian)(thf)Al–Al(thf)(dpp-bian)] (3), with N2O affords oxo-bridged [(dpp-bian)Al(thf)(μ-O)Al(thf)(dpp-bian)] (4). The addition of carbon dioxide to compound 2 leads to the formation of carbonate [(dpp-bian)Al(μ-O)(μ-CO3)Al(dpp-bian)] (5). Diamagnetic derivatives have been characterized by 1H NMR spectroscopy and paramagnetic compounds by electron paramagnetic resonance spectroscopy; their molecular structures have been established by single-crystal X-ray analysis.

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Borane reduction of carbon dioxide bound to diimine-supported aluminum hydrides

Cited by 7 publications

References 29 publications

Hydroboration of a Diolate Complex Obtained by Carbon Dioxide Capture with Acenaphthenediimine Aluminum Hydride

Hydroboration of a Diolate Complex Obtained by Carbon Dioxide Capture with Acenaphthenediimine Aluminum Hydride

Catalytic hydroboration of carbon dioxide and cyclohexyl isocyanate with diimine zinc hydrides

Reduction of Nitrous Oxide and Binding of Carbon Dioxide by Acenaphthene-1,2-diimine Aluminum Compounds

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