Quantum chemical study of the electron affinity of the diimino derivatives of mono- and polycyclic organic molecules

Baranovski, V. I.; Denisova, A. S.; Kuklo, L. I.

doi:10.1016/j.theochem.2005.10.056

Cited by 10 publications

(12 citation statements)

References 9 publications

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“…The Ga–N distances are noticeably longer than those in the starting material [(dpp-Bian)Ga–Ga(dpp-Bian)] (ave. 1.86 Å). This fact is consistent with a decrease in the bonding nature of the molecular orbitals of these bonds. , The Ga–B bond length [2.119(2) Å] is somewhat longer than expected from the sum of the covalent radii of the gallium (1.22 Å) and boron (0.84 Å) atoms . This Ga–B bond is similar to that in the β-ketoiminate complex [HC[MeC(2,6- i Pr 2 C 6 H 3 )] 2 NGa → B(C 6 F 5 ) 3 ] [2.156(1) Å] and the tris(pyrazolyl)borate complex [HB(Pz) 3 Ga → B(C 6 F 5 ) 3 ] [Pz = hydrotris(pyrazolyl)borate; 2.177(3) Å] .…”

Section: Results and Discussionsupporting

confidence: 70%

“…This fact is consistent with a decrease in the bonding nature of the molecular orbitals of these bonds. 86,87 The Ga−B bond length [2.119(2) Å] is somewhat longer than expected from the sum of the covalent radii of the gallium (1.22 Å) and boron (0.84 Å) atoms. 88 This Ga−B bond is similar to that in the β-ketoiminate 71 and the tris(pyrazolyl)borate complex [HB-(Pz) 3 Ga → B(C 6 F 5 ) 3 ] [Pz = hydrotris(pyrazolyl)borate; 2.177(3) Å].…”

Section: Reactions Of [(Dpp-bian)aletmentioning

confidence: 99%

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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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Section: Results and Discussionsupporting

confidence: 70%

Section: Reactions Of [(Dpp-bian)aletmentioning

confidence: 99%

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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“…This qualitative prediction receives support from the DFT calculated (B3LYP/6-31+G(d) basis set) electron affinities of model BIAN ligands that reveal values of the order of 1.0 eV for addition of the first electron. 28 The magnitude of the electron affinity is only slightly sensitive to the presence or absence of the imino functionalities.…”

Section: General Properties Of R-bian Ligandsmentioning

confidence: 99%

Recent developments in the coordination chemistry of bis(imino)acenaphthene (BIAN) ligands with s- and p-block elements

2009

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Bis(imino)acenaphthenes (BIAN) have been known for many years. However, it is only since the 1990s that such compounds have been recognized as robust ligands for the support of catalytically active transition metal centers. More recently, the unique stereoelectronic properties of the BIAN ligand class are beginning to be appreciated and exploited for some fascinating new developments in synthetic, structural and catalytic s- and p-block chemistry.

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“…The ligand dpp‐bian, which is a π‐acceptor of reasonable strength, has a first reduction potential of –1.0 V, and is expected to be present as a radical anion. The relatively low value of the 47,49 Ti hyperfine coupling (HFC) constant, accompanied by a g‐factor very close to 2, lead us to suggest that the structure of the metal complex 4 in toluene solution is A .…”

Section: Resultsmentioning

confidence: 99%

“…Kaim [14] reported on a series of titanium isopropoxido complexes with π-acceptor substrates, including α-diimines, where paramagnetic compounds were described as Ti III or Ti IV /radical species, [15] depending on the reduction potential of the ligand. The ligand dpp-bian, which is a π-acceptor of reasonable strength, has a first reduction potential of -1.0 V, [16] and is expected to be present as a radical anion. The relatively low value of the 47,49 Ti hyperfine coupling (HFC) constant, accompanied by a g-factor very close to 2, lead us to suggest that the structure of the metal complex 4 in toluene solution is A.…”

Section: Solution Spectroscopy Studies Of Complexes 2-4mentioning

confidence: 99%

Four‐ and Five‐Coordinate Titanium(IV) Complexes Supported by the dpp‐bian Ligand in ROP of L‐Lactide

et al. 2019

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A titanium(IV) alkoxido complex, (dpp-bian)Ti(OBn) 2 (2), as well as alkoxido chlorido complexes (dpp-bian)-TiCl(OCH 2 CH 2 OMe) (3) and (dpp-bian)TiCl 2 OBn (4), were synthesized from the titanium(IV) dichloride precursor [(dppbian)TiCl 2 ] 2 (1) by exchange with corresponding sodium salts (comps. 2 and 3) or by the alcoholysis with BnOH (comp. 4). The compounds 2-4 were fully characterized by elemental analysis, NMR or EPR, and IR spectroscopy. Molecular structures of the metal complexes in the solid state have been determined[a] G.A. Razuvaev

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Quantum chemical study of the electron affinity of the diimino derivatives of mono- and polycyclic organic molecules

Cited by 10 publications

References 9 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

Recent developments in the coordination chemistry of bis(imino)acenaphthene (BIAN) ligands with s- and p-block elements

Four‐ and Five‐Coordinate Titanium(IV) Complexes Supported by the dpp‐bian Ligand in ROP of L‐Lactide

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