Hydrogen-bonded dialkylcarboxamide cations and their dihalogenohalogenates

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Abstract

Molecular geometry, electron structure and thermodynamic parameters for a representative group of tertiary amides and bis(amide)hydrogen cations were computed by density functional theory at ωB97X-V/dgdzvp//ωB97X/dgdzvp level, trihalide salts of these cations were synthesized, and NMR manifestations of short hydrogen bond in these cations were experimentally demonstrated. With a vocabulary of computational techniques, a number of intramolecular noncovalent interactions such as H···O+···H, C–H···O, C–H···Н–С were revealed, and the role of these interaction in the stabilization of hemiprotonated amides and their saline forms evaluated.

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О. М. Zarechnaya

L. M. Litvinenko Institute of Physical Organic and Coal Chemistry

Email: mikhail0vvasilii@yandex.ru
ORCID iD: 0000-0002-6069-3967
Russian Federation, Donetsk, 283048

V. А. Mikhailov

L. M. Litvinenko Institute of Physical Organic and Coal Chemistry

Author for correspondence.
Email: mikhail0vvasilii@yandex.ru
ORCID iD: 0000-0002-4184-1805
Russian Federation, Donetsk, 283048

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Supplementary files

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2. Scheme 1. R2 = R3 = Me, R1 = H (2), Me (3–5), Et (7), i-Pr (8), tert-Bu (9), NMe2 (11, 12); R2 = R3 = Et, R1 = Me (6); R1 + R2 = –(CH2)3–, R3 = Me (10); [X-Y-Z]– = [Br-I-Br]– (2, 3, 12), [Cl-I-Cl]– (4), [Cl-I-Br]– (5), [Br-Br-Br]– (6–11).

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3. Fig. 1. Dependence of the chemical shift of the bridging proton of dihaliodates 1, 3–5, 12 (a) and 2, 6–9 (b) on the concentration (mol/kg solvent). Chloroform, 25°C.

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4. Scheme 2. R1 = Me, R2 = R3 = Et (13, 20); R2 = R3 = Me, R1 = Et (14, 21), i-Pr (15, 22), tert-Bu (16, 23), NMe2 (18, 25); R1 + R2 = –(CH2)3–, R3 = Me (17, 24).

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5. Fig. 2. Preferred conformations of ethyl substituents in the calculated structures of N,N-diethylacetamide 13 and N,N-dimethylpropanamide 14.

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6. Fig. 3. Orientation of β-methyl groups and short H H contacts in the calculated structures of N,N-dimethylisobutyramide 15 and N,N-dimethylpivalamide 16.

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7. Fig. 4. General appearance of molecules of N-methylpyrrolidinone 17 and N,N,N′,N′-tetramethylurea 18.

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8. Fig. 5. General appearance of the cations bis(N,N-diethylacetamide)hydrogen 20 and bis(N,N-dimethylpropanamide)hydrogen 21.

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9. Fig. 6. General appearance of the cations bis(N,N-dimethylisobutyramide)hydrogen 22 and bis(N,N-dimethylpivalamide)hydrogen 23.

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10. Fig. 7. General appearance of the cations bis(N-methylpyrrolidinone)hydrogen 24 and bis(N,N,N′,N′-tetramethylurea)hydrogen 25.

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11. Fig. 8. ELF and LOL representations for free amide molecules 13–18. Monosynaptic basins are highlighted in green, disynaptic basins in red.

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12. Fig. 9. Distribution of molecular electrostatic potential in free molecules of amides 13–18.

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13. Fig. 10. RDG representation of free amide molecules 13–18.

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14. Fig. 11. Intramolecular C–H H–C interactions in the molecules of amides 15 and 16. Critical binding points with the signature (3,–1) are highlighted in orange, and ring critical points with the signature (3,+1) are highlighted in brown.

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15. Fig. 12. Distribution of electron density along the Cα–Hc bond of amide 15 (a) and the relief of electron density between the attractors of the Hb and Hc atoms of amide 15 (b).

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16. Fig. 13. ELF representations for calculated cations 19–25.

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17. Fig. 14. RDG representation of cations 19–25.

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18. Fig. 15. Bonding interactions in cations 19–25. Critical points of O H bonding with the signature (3,–1) and the (C–H)A OB bonding pathways are highlighted in orange; cyclic critical points (3,+1) are highlighted in brown.

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19. Fig. 16. Curved path of H32 H35 binding in cation 22, connecting C–Hd atoms of parts A and B (a) and a map of the electron density relief in the region of the attractors of hydrogen atoms H32 and H35 (b). The binding path is highlighted in blue, the critical binding point (3,–1) is highlighted in orange, and the cyclic point (3,+1) is highlighted in brown.

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