Attractive Interaction Caused by the Linear F···Se−C Alignment in Naphthalene Peri Positions

Abstract

The X-ray crystallographic analysis of 8-fluoro-1-(p-anisylselanyl)naphthalene (1) revealed that the F and Se atoms and the ipso-carbon of the p-anisyl group (C(An)) aligned linearly. The F atom and the Se-C(An) bond lay on the naphthyl plane: the nonbonded distance between F and Se atoms was 2.753(3) Å and the FSeC(An) angle was 175.0(1)°. Ab initio MO calculations with the 6-311++G(3df,2pd) basis sets performed on the model compound of 1, HF‚‚‚SeH 2 , where the aryl groups of 1 were replaced by hydrogens. The calculations exhibited that the energy minimum was achieved when the F, Se, and C(An) atoms aligned linearly. Charge transfer in the formation of HF‚‚‚SeH 2 was suggested to occur from F to SeH 2 on the basis of natural population analysis, which supported the np x (F)-σ*(Se-C(An)) interaction.

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

“…The P→Sb derivatives with either a less Lewis basic donor ( K ) or less Lewis acidic acceptor ( 3 , 3‐Mes and 4 ) adopt structure Y , which is driven by a formation of the n(P)→σ*(Sb–R) 3c–4e interaction. Indeed, 3c–4e bonding has been shown to drive conformational preferences in a wide range of peri ‐substituted species, stretching from 1‐fluoro‐8‐anisylselenyl naphthalene, M ,4a, 18 to heteroleptic bis(phosphino)acenaphthene, N (Figure 4). 19…”

Intramolecular Nonbonded Interactions Between Divalent Selenium Centers with Donor and Acceptor Substituents

“…It was found that the 77 Se NMR chemical shift (δ Se ) is sensitive to the environment around the Se center, and its shift can be used as a measure of the strength of the nonbonding interactions of Se with other atoms with lone pairs. [24][25][26] To explore whether there are intramolecular nonbonding interactions between the Se centers of 1-3 in solution, first we compared the 77 Se NMR chemical shifts of 1 with the model compounds 12-16 shown in Figure 5. Originally we thought that methyl phenyl selenide (16) (δ Se = 199 ppm) [26] might be a good model for 1.…”

peri-Interactions in Naphthalenes, 4 [1]. Hypercoordination in 8-Dimethylamino-naphth-1-yl Phosphorus Compounds

“…A model calculation with d(F-C) = 135.6 pm (as in Ph-F [93]), d(Se-CPh) = 191.2 pm (as in Ph-Se-Me [94]) and C-Se-C 99.6° (as in Ph-Se-Me [94]) yields the angle F-Se-Caryi = 176.9°, i. e. closer to 180° than the experimental angles. -ab initio calculations performed on the system H-F...SeH2[81] fail to take into account the geometric peculiarities of the naphthalene system and are, therefore, not helpful (cf. G. P. Schiemenz, R. Bukowski, L. Eckholtz, B. Vamskühler[1], note 41).…”

“…0°) [78] 120.2°125.5°120.6°+6.3°[45b] 123.2°122.3°116.6°+2.1°[33] 123.9°122.5°117.4°+3.8°[33] 121.6°122.4°117.4°+ 1.4°[33] 124.8°123.7°117.0°+5.5°[34] 125.5°121.7°115.9°+3.1°[33] 123.4°124.4°113.2°+ 1.0°[33] 124.0°124.3°114.4°+2.7°[33] 123.1°124.4°115.0°+2.5°[79] 125.4°125.1°118.4°+8.9°[34] 124.2°123.4°114.8°+2.4°[34] 124.2°126.3°121.6°+ 12.1°[34] 124.7°126.2°121.0°+ 11.9°1 21.6°125.5 121.6°+8.7°[44b] 123.1°125.5°123.1°+ 11.7°1 24.5°125.3°123.0°+ 12.8°[44b] 124.0°126.5°126.3°+ 16.8°[80] 120.5°125.9°119.1°+5.5°[81] 120.7°125.6°118.7°+5.0°-…”