Aluminum hydrides with radical-anionic and dianionic acenaphthene-1,2-diimine ligands

Соколов, В. Г.; Koptseva, Tatyana S.; Moskalev, M. V.; Piskunov, A. V.; Самсонов, М. А.; Fedushkin, Igor L.

doi:10.1007/s11172-017-1926-1

Cited by 21 publications

(37 citation statements)

References 26 publications

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“…Thus, the reaction of 1 with 1,3-diisopropyl-4,5-dimethylimidazol-2- Recently, we prepared aluminum hydrides supported with radical anion as well as dianion of dpp-Bian. 36,37 Surprisingly, a treatment of hydride (dpp-Bian)AlH(THF) (2) with HOC 6 H 2 -2,6-tBu-4-Me proceeds with protonation of one of the nitrogen atoms of dpp-Bian, while hydride ligand remains unaffected. 38 To study an influence of the spectator donor ligand on reactivity of H − and (dpp-Bian) 2− we attempted replacement of THF with an electron-rich NHC molecule.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…38 To study an influence of the spectator donor ligand on reactivity of H − and (dpp-Bian) 2− we attempted replacement of THF with an electron-rich NHC molecule. Complex (dpp-Bian)AlH(iPr 2 Im Me ) (6) was synthesized by the reaction of mononuclear aluminum hydride (dpp-Bian)-AlH(THF) (2) 36 with iPr 2 Im Me (Scheme 5). The reaction proceeds in toluene at 50 °C within 15 min.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…This value is significantly different from those for ketiminate derivative {HC(C(CH 2 )NAr)(CMeNAr)}AlH(iPr 2 Im Me ) (1809 cm −1 ) 39 as well as for starting 2 (1864 cm −1 ). 36 The 1 H NMR spectrum of compound 6 (Figure 1) contains the signals of coordinated dpp-Bian and iPr 2 Im Me ligands. In tetrahedral coordination environment the hydride and iPr 2 Im Me ligands are located above and below the 1,3,2diazametallacycle plane.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The Al(1)−H(1) bond length (1.523(17) Å) is close to that in compound 2 (1.533(17) Å) and to those values other aluminum hydrides. 36,49 DFT Calculation of Compounds 1−3 and 6. The DFTcalculated geometries of compounds 1, 2, 3, and 6 (Figure 6) are in good agreement with those determined by X-ray crystallography.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Wiberg bond indexes (WBIs) in natural atomic orbitals for diimine fragments in 1, 26 2, 36 Thus, in contrast to complex 1, a molecule of complex 3 has a nonzero dipole moment (μ x = 1.31, μ y = −0.85, μ z = 8.06, μ = 8.21). Interestingly, the bond order Al−C(carbene) in 6 (0.46) is twice as high as bond order Al−O(THF) (0.21) in 2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione

et al. 2019

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The reaction of dialane (dpp-Bian)Al−Al(dpp-Bian) (1) (dpp-Bian is dianion of 1,2-bis [(2,6diisopropylphenyl)imino]-acenaphthene) with 1 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (iPr 2 Im Me ) results in the Al-carbene adduct (dpp-Bian)(iPr 2 Im Me )Al− Al(dpp-Bian) (3). In the course of the reaction of dialane 1 with 2 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2thione (iPr 2 Imt Me ) a half of the thione amount undergoes a cleavage of sulfur−carbon double bond. In the product (dpp-Bian)(iPr 2 Im Me )Al(μ-S)Al(iPr 2 Imt Me )(dpp-Bian) (4) aluminum atoms coordinate carbene as well as thione ligands. Compound 4 is thermally robust: no reduction of CS bond in thione moiety by the dpp-Bian ligands could be observed in toluene for 24 h at 100 °C. Complex {(dpp-Bian)(iPr 2 Im Me )Al} 2 (μ-S) (5) was isolated from the reaction of dialane 1, iPr 2 Im Me , and iPr 2 Imt Me (1:1:1). The reaction of mononuclear (dpp-Bian)AlH(THF) (2) (THF = tetrahydrofuran) affords compound (dpp-Bian)AlH(iPr 2 Im Me ) (6). Compounds 3−6 were characterized by 1 H NMR and IR spectroscopy; their molecular structures were established by single-crystal X-ray analysis.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione

et al. 2019

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BIAN‐Aluminium‐Catalysed Imine Hydrogenation

et al. 2022

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On the occasion of the 60 th birthday of Matthias BellerHydrogenations have been dominated by transition metal catalysis, while the use of more abundant and inexpensive main group metal catalysts has remained a great challenge. Here, a bimetallic Li/Al dihydride was successfully applied to catalytic hydrogenations of imines. The catalyst [( Dipp BIAN)Al(μ-H) 2 Li-(OEt 2 ) 2 ] was easily prepared from the 2e-reduced BIAN derivative and LiAlH 4 .

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