peri-Interactions in naphthalenes, 13 8-Dimethylamino-naphth-1-yl carbinols as model systems for potential N→Si/P interactions

Dominiak, Paulina M.; Petersen, Sönke; Schiemenz, Berthold; Schiemenz, G. P.; Woźniak, Krzysztof

doi:10.1016/j.molstruc.2005.04.042

Cited by 9 publications

(12 citation statements)

References 73 publications

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“…In polyatomic molecules, bond lengths and natural bond angles create a multitude of interatomic distances much smaller than Σr(vdW) which are a matter of course rather than evidence for bonding [15]. The argument is not restricted to rigid structures (as, e. g., to the ortho-positions of 1,2-disubstituted benzenes and the peri-positions of 1,8-disubstituted naphthalenes [16,17]).…”

Section: Discussionmentioning

confidence: 99%

The Sum of van der Waals Radii – A Pitfall in the Search for Bonding

Schiemenz

2007

Zeitschrift Für Naturforschung B

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The most widely used criterion for the evaluation of chemical bonding, especially of weak bonding, are interatomic distances shorter than the sum of the van der Waals radii, d(X···Y) < Σr(vdW)[X, Y]. The shortcomings of these radii are, however, so serious, that illicit conclusions are easily arrived at. It is proposed to discard the 'shorter than Σr(vdW)' criterion altogether and to rely on alternative criteria.

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Section: Discussionmentioning

confidence: 99%

The Sum of van der Waals Radii – A Pitfall in the Search for Bonding

Schiemenz

2007

Zeitschrift Für Naturforschung B

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“…The peri-X-Y interaction in 1,8-disubstituted naphthalenes has been known for a long time (Balasubramaniyan, 1966) and is of interest because the enforcing geometry results in a close interatomic XÁ Á ÁY contact, which is much shorter than the sum of the van der Waals radii for all atoms other than H. This provides an ideal environment in which to examine interesting weak interactions such as the 'N)Si/P donor-acceptor interaction' (which potentially involves hypercoordination at the Si/P atom; see, for example, Schiemenz & Nä ther (2002), Dominiak et al (2005) andrefs therein, andO'Leary &Wallis (2006). In terms of characterizing such interactions by AIM methods, the most important evidence lies in the presence or absence of a bond path (Bader, 1998).…”

Section: Figurementioning

confidence: 99%

Weak intra- and intermolecular interactions in a binaphthol imine: an experimental charge-density study on (±)-8′-benzhydrylideneamino-1,1′-binaphthyl-2-ol

Farrugia

Kočovský

Senn

et al. 2009

Acta Crystallogr Sect B

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The charge density in (+/-)-8'-benzhydrylideneamino-1,1'-binaphthyl-2-ol (1) has been studied experimentally using Mo Kalpha X-ray diffraction at 100 K, and by theory using density-functional thoery (DFT) calculations at the B3LYP/6-311++G** level. The nature of the weak intramolecular peri-C...N, CH...pi, H...H and C(pi)...C(pi) interactions has been examined by topological analysis using the Quantum Theory of Atoms in Molecules (QTAIM) approach. An analysis of the density rho(r), the Laplacian of the density inverted Delta(2)rho(r(b)) and other topological properties at the bond-critical points were used to classify these interactions. The study confirms the presence of the intramolecular CH...pi interaction in (1), which was previously suspected on geometrical grounds. An analysis of the ellipticity profiles along the bond paths unambiguously shows the pi-delocalization between the imine unit and one N-phenyl group. The weak intermolecular interactions in the crystal of (1) were examined experimentally and theoretically through the pairwise interactions of the seven independent dimeric pairs of (1) responsible for the set of unique intermolecular interactions, and also through examination of the Hirshfeld surface d(norm) property. The theoretical dimeric-pair calculations used the BLYP-D functional which supplements the exchange-correlational functional with an empirical dispersion term to provide a more accurate determination of the energies for the weak intermolecular interactions.

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“…super basicity, 7-11 vibrational spectrum, 12 including theoretical 13 NMR spectroscopy (chemical shifts and spin-spin coupling constants), [14][15][16][17][18] and experimental X-ray diffraction studies. 20,21 It was a natural progression that the success of DMAN and its derivatives lead to the study of the effect of replacement of the N atoms by other atoms of the same period 15, the pnicogen or pnictogen period, the contiguous ones being P and As. 20,21 It was a natural progression that the success of DMAN and its derivatives lead to the study of the effect of replacement of the N atoms by other atoms of the same period 15, the pnicogen or pnictogen period, the contiguous ones being P and As.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Sánchez‐Sanz

Trujillo

Alkorta

et al. 2014

Phys. Chem. Chem. Phys.

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A computational study of the intramolecular pnicogen bond in 1,8-bis-substituted naphthalene derivatives (ZXH and ZX2 with Z = P, As and X = H, F, Cl, and Br), structurally related to proton sponges, has been carried out. The aim of this paper is the study of their structural parameters, interaction energies and electronic properties such as electron density on the intramolecular interaction. The calculated geometrical parameters associated to the P···P interaction are in reasonably good agreement with the crystal structures found in a CSD search, in particular those of the halogen derivatives. Isodesmic reactions where the 1,8-bis-substituted derivatives are compared to monosubstituted derivatives have been calculated, indicating that the 1,8 derivatives are more stable than the monosubstituted ones for those cases with X-Z···Z-X and F-Z···Z-H alignments. Electron densities and Laplacians at the BCP on the pnicogen interactions suggest that they can be classified as pure closed shell interactions with a partial covalent character. Electron density shift maps are consistent with the results for intermolecular pnicogen interactions. Relationships between interatomic distance and electron density at the bond critical points and between interatomic distance and the orbital charge transfer stabilization energies have been found.

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peri-Interactions in naphthalenes, 13 8-Dimethylamino-naphth-1-yl carbinols as model systems for potential N→Si/P interactions

Cited by 9 publications

References 73 publications

The Sum of van der Waals Radii – A Pitfall in the Search for Bonding

The Sum of van der Waals Radii – A Pitfall in the Search for Bonding

Weak intra- and intermolecular interactions in a binaphthol imine: an experimental charge-density study on (±)-8′-benzhydrylideneamino-1,1′-binaphthyl-2-ol

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

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