The rotational spectrum and molecular structure of the furan–HCl complex

Shea, J. A.; Kukolich, Stephen G.

doi:10.1063/1.445178

Cited by 54 publications

(28 citation statements)

References 15 publications

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“…On the other hand, the component of the quadrupole moment perpendicular to the ring plane is large and negative in each case, as expected from the extension of the p system above and below the plane of the ring, but is largest for thiophene. All of this evidence about the electronic distributions is consistent with the observed structures of furan´´´HCl [33] and pyridine´´´HCl, [37] which are as predicted by rule 3, but suggests that the p system may be more nucleophilic than is the n pair with respect to HCl, as well as to ClF, when the Lewis base changes to thiophene.…”

Section: P-electron Donor Complexes B´´ćsupporting

confidence: 79%

See 1 more Smart Citation

π-Electron “Donor-Acceptor” Complexes B⋅⋅⋅ClF and the Existence of the “Chlorine Bond”

Legon

1998

Chem. Eur. J.

140

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Section: P-electron Donor Complexes B´´ćsupporting

confidence: 79%

“…The geometry of furan´´´HCl [33] is shown in Figure 8. It has C 2v symmetry, and the HCl molecule lies along the C 2 axis of furan, forming a hydrogen bond to the n pair on oxygen.…”

Section: P-electron Donor Complexes B´´ćmentioning

confidence: 99%

π-Electron “Donor-Acceptor” Complexes B⋅⋅⋅ClF and the Existence of the “Chlorine Bond”

Legon

1998

Chem. Eur. J.

140

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“…[ * ] Rotational spectroscopy shows [39] that HCl is hydrogen-bonded to the furan oxygen atom along the C 2 symmetry axis of the molecule. We expect that furan is also an oxygen base towards 4-fluorophenol (and not a π base as assumed in ref.…”

Section: Structure؊hydrogen-bond Basicity Relationshipsmentioning

confidence: 99%

The Hydrogen-Bond Basicity pKHB Scale of Peroxides and Ethers

1998

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Using 4‐fluorophenol as a reference hydrogen‐bond donor, equilibrium constants, Kf, for the formation of 1:1 hydrogen‐bonded complexes have been obtained by FTIR spectrometry for 39 ethers of widely different structure (cyclic and acyclic ethers, crown ethers, glymes, acetals, orthoesters, and disiloxane) and 3 peroxides, in CCl4 at 298 K. The pKHB scale of monoethers extends from 1.44 for 2,3‐diadamant‐2‐yloxirane to –0.53 for hexamethyldisiloxane. The main effects explaining the variation of the hydrogen‐bond basicity of sp3 oxygen atoms are (i) the electron‐withdrawing field‐inductive effect [e.g. in (CF3)2CHOMe], (ii) the electron‐withdrawing resonance effect (e.g. in EtOCH=CH2) (iii) the steric effect (e.g. in tBu2O), (iv) the lone‐pair–lone‐pair repulsion (e.g. in cyclic peroxides), and (v) the cyclization giving the basicity order: oxetane > tetrahydrofuran > tetrahydropyran > oxirane. A spectroscopic scale of hydrogen‐bond basicity is constructed from the infrared frequency shift Δν(OH) of methanol hydrogen‐bonded to peroxides and ethers. The thermodynamic pKHB scale does not correlate with the ν(OH) scale because of (i) statistical effects in polyethers and peroxides (ii) secondary hydrogen‐bond acceptor sites (e.g. in benzyl ether), (iii) variations of the s character of oxygen lone pairs either by conjugation or cyclization, (iv) steric effects, (v) lone‐pair–lone‐pair repulsions, and (vi) anomeric effects. The ν(OH···O) band shape reveals two stereoisomeric complexes, the most stable being tetrahedral at the ether oxygen atom.

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“…The last complex was between HCl and furan where HCl formed a hydrogen bond to oxygen in furan in its plane. 8,9 We report here the first observation of the pyridine-CO complex through its microwave spectrum. Rather unexpectedly, CO was found not to bind above the plane to the aromatic system of pyridine, but in the molecular plane of pyridine and not simply along its C 2 axis.…”

Section: Introductionmentioning

confidence: 89%

The microwave spectrum and structure of the pyridine–CO complex

Bettens¹,

Bauder²

1995

The Journal of Chemical Physics

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Rotational spectra of five isotopomers of the pyridine-CO complex with D, 13 C, 15 N, and 18 O have been measured over the 8 -18 GHz frequency range. Rotational constants, centrifugal distortion constants, and 14 N quadrupole coupling constants have been fitted to the measured transition frequencies of each isotopomer. Two different structures have been found to be compatible with the moments of inertia of all isotopomers. Both have CO lying in the plane of pyridine approaching simultaneously N and ortho-H but with two different orientations of CO.

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The rotational spectrum and molecular structure of the furan–HCl complex

Abstract: Articles you may be interested inEvidence of an isomeric pair in furan…HCl: Fourier transform infrared spectroscopy and ab initio calculations

Cited by 54 publications

References 15 publications

π-Electron “Donor-Acceptor” Complexes B⋅⋅⋅ClF and the Existence of the “Chlorine Bond”

π-Electron “Donor-Acceptor” Complexes B⋅⋅⋅ClF and the Existence of the “Chlorine Bond”

The Hydrogen-Bond Basicity pKHB Scale of Peroxides and Ethers

The microwave spectrum and structure of the pyridine–CO complex

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