Nature of the E⋯E′ interactions (E, E′ = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: experimental and theoretical investigations

Published on Sep 16, 2019in New Journal of Chemistry3.591
· DOI :10.1039/C9NJ02198A
Satoko Hayashi24
Estimated H-index: 24
(Wakayama University),
Manabu Uegaito1
Estimated H-index: 1
(Wakayama University)
+ 5 AuthorsMao Minoura15
Estimated H-index: 15
(Rikkyo University)
Sources
Abstract
The intrinsic dynamic and static natures of the E⋯E′ interactions at the 1,8-positions of 1-(MeE)–8-(MeE′)C10H6 [1a–1f (E ≠ E′) and 1g–1j (E = E′)] were elucidated with QTAIM-DFA, after structural determination of 1-(PhE)–8-(PhE′)C10H6 (3a–3f), where (E, E′: x) = (O, S: a), (O, Se: b), (O, Te: c), (S, Se: d), (S, Te: e), (Se, Te: f), (O, O: g), (S, S: h), (Se, Se: i) and (Te, Te: j) (χE ≥ χE′). While the AB structures are confirmed for 3a, 3b and 3d–3f, which consist of the np(E)⋯σ*(E′–CPh) interactions, the structure was BB for 3c, where the E–CR/E′–CR (R = Ph) bond is perpendicular to the naphthyl plane in A and it is placed on the plane in B. While the AB structures are determined by the p(E)–π(Ph) conjugations, the BB structure is by the crystal packing effect. The BA structure with np(E′)⋯σ*(E–CPh) was not detected. While the nature of a typical hydrogen bond with covalency was predicted for BB, AA and BA, with the CT-MC (molecular complex formation through charge transfer) nature for AB in 1e and 1f (R = Me for E–CR/E′–CR), the CT-MC nature was predicted for all conformers of 1j, for example. NBO analysis for 1a–1f revealed that the acceptor orbitals contribute much more than the donor orbitals and the order is σ*(O–CMe: <0.5 kcal mol−1) ≪ σ*(S–CMe: ≈5 kcal mol−1) ≪ σ*(Se–CMe: ≈10 kcal mol−1) ≪ σ*(Te–CMe: ≈16 kcal mol−1) for np(S), np(Se) and np(Te). The E(2) values proportionally correlate to Cii−1 for AB and/or BA of 1a–1j, if analyzed separately for σ*(S–C), σ*(Se–C) and σ*(Te–C).
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In a recent publication, the interpretation of Braunschweig's diboryne NHC–BB–NHC as a true triple bond is questioned. The analysis by Koppe and Schnockel is based, inter alia, on the calculation of rigid coupling force constants. Nevertheless, since it is known for a long time that the use of rigid force constants as bond strength descriptors is by no means straightforward, we recomputed the rigid force constants for a model diboryne, applying different coordinate systems and compared the value...
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The new computer program SHELXT employs a novel dual-space algorithm to solve the phase problem for single-crystal reflection data expanded to the space group P1. Missing data are taken into account and the resolution extended if necessary. All space groups in the specified Laue group are tested to find which are consistent with the P1 phases. After applying the resulting origin shifts and space-group symmetry, the solutions are subject to further dual-space recycling followed by a peak search a...
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#1Takeshi Noro (Hokkaido University)H-Index: 25
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Last. Toshikatsu Koga (MuIT: Muroran Institute of Technology)H-Index: 30
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Synthetic and bonding aspects of heavier Group 15 (P, As, Sb, Bi) and 16 (S, Se, Te) peri-substituted naphthalenes, are discussed in this review. An important and unifying feature of the chemistry of these systems is the lively discussion about the nature of the interaction between peri-atoms. Are atoms bonded when they are closer than the sum of their van der Waals radii? Is there any (weak) bonding, or just a strained repulsive interaction? Positioning atoms of Group 15 and 16 at the naphthale...
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A method to evaluate the dynamic nature of interactions is proposed based on the AIM dual functional analysis. Normal coordinates of internal vibrations (NIV) are employed to generate the perturbed structures necessary for the analysis. H b (r c ) are plotted versus H b (r c ) ― V b (r c )/2 [= (ħ 2 /8m)∇ 2 ρ b )(r c )] at bond critical points for the purpose. The plots are represented by the polar (R, θ) coordinate. Each plot for an interaction shows a specific curve, which is expressed by (θ p...
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#1Fergus R. Knight (St And: University of St Andrews)H-Index: 17
#2Amy L. Fuller (St And: University of St Andrews)H-Index: 17
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Four novel 1,8-disubstituted naphthalene derivatives 4–7 that contain chalcogen atoms occupying the peri positions have been prepared and fully characterised by using X-ray crystallography, multinuclear NMR spectroscopy, IR spectroscopy and MS. Molecular distortion due to noncovalent substituent interactions was studied as a function of the bulk of the interacting chalcogen atoms and the size and nature of the alkyl group attached to them. X-ray data for 4–7 was compared to the series of known 1...
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We present an extension to the theory of compliance matrices, which is valid for arbitrary nonstationary points on the potential energy hypersurface. It is shown that compliance matrices computed as the inverse of the covariant Hessian matrix obey the same invariance properties with respect to different internal coordinate systems as they do for stationary points. Furthermore, we demonstrate how the computation of compliance matrices in arbitrary sets of redundant internal coordinates starting f...
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Abstract null null Two new selenated ligands: (S)-BnSeCH2CH(Bn)N = CH-C6H3-3-OCH3-2-OH ((S)-L1H) and (S)-BnSeCH2CH(Bn)NH-CH2-C6H3-3-OCH3-2-OH ((S)-L2H) incorporating ortho-vanillin moiety and their respective palladium(II) complexes (S)-1 and (S)-2 were synthesized in a high-yielding procedures. All compounds were characterized by various spectroscopic techniques such as 1H, 13C{1H} NMR, FT-IR, and UV–Visible. Further, the elemental and single crystal X-ray diffraction analyses of complexes show...
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This article reviews the history and the current state of knowledge concerning the ability of the heavy chalcogen atoms S and Se, and to some extent Te, to participate in a H-bond as either proton donor or acceptor. These atoms are nearly as effective proton acceptors as O, and only slightly weaker as donor. They can also participate in chalcogen bonds where they act as electron acceptors from a nucleophile. These bonds rapidly strengthen as the chalcogen atom becomes larger: S < Se < Te, or if ...
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#1Satoko Hayashi (Wakayama University)H-Index: 24
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The intrinsic dynamic and static nature of G–*–E–*–Y σ(3c–4e) interactions was elucidated with the quantum theory of atoms in molecules dual functional analysis (QTAIM-DFA), employing o-MenGCH2C6H4EY (MenG = Me2N and MeE; E = O, S, Se and Te; Y = F, Cl, Br, I, EMe and Me). Asterisks (*) are employed to emphasize the existence of bond critical points (BCPs) on the bond paths (BPs), corresponding to the interactions in question. Data from the fully optimized structure correspond to the static natu...
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