A study of the basis set dependence of the geometry and proton affinity for a series of vinyl ethers and vinyl sulfides

2009 ◽  
Vol 36 (S23) ◽  
pp. 453-463
Author(s):  
K. Ösapay ◽  
L. Hevesi ◽  
J. Delhalle
Keyword(s):  
Proton Affinity ◽  
Basis Set ◽  
Vinyl Ethers ◽  
Vinyl Sulfides

Specific intramolecular interactions C-H···N in heteroaryl vinyl ethers and heteroaryl vinyl sulfides studied by 1H, 13C, and 15N NMR spectroscopies and by ab initio calculations on molecular structures as well as on nuclear shieldings

1999 ◽  
Vol 77 (4) ◽  
pp. 416-424 ◽  
Author(s):  
Andrei V Afonin ◽  
Alexander V Vashchenko ◽  
Tatsuya Takagi ◽  
Atsuomi Kimura ◽  
Hideaki Fujiwara
Keyword(s):  
Hydrogen Bonding ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Intramolecular Interaction ◽  
Intramolecular Hydrogen Bonding ◽  
Basis Set ◽  
Vinyl Ethers ◽  
Vinyl Sulfides ◽  
Intramolecular Hydrogen ◽  
Vinyl Group

1H,13C, and 15N NMR spectra have been measured for a series of isostructural aryl (heteroaryl) vinyl sulfides and compared with analogues of vinyl ethers. It was found that "intramolecular interaction" of the α-hydrogen of the vinyl group with endocyclic nitrogen takes place in 2-vinylthiopyridines. This is in common with the findings for 2-vinyloxypyridine and the intramolecular interaction is shown to have a profile characteristic of hydrogen bonding. Also, the NMR spectral data show that this type of interaction is more intense (~1.5 times) in 2-vinyloxypyridine than in 2-vinylthiopyridine. This is probably due to the greater electronegative effect of oxygen compared to that of sulfur. To discuss these findings further in detail, ab initio calculations have been made, and the conformational energy map and the NMR chemical shifts have been discussed. The ab initio calculations, which were carried out on the D95++(d,p) basis set at the B3LYP level, confirm the planar structure of 2-vinyloxy- and 2-vinylthiopyridines, while other analogues of these ethers and sulfides were essentially nonplanar. Gauge-Independent Atomic Orbital (GIAO) calculations of the shielding constants, based on the same basis set, support the extraordinary low-field shift of the α-hydrogen in the vinyl group when it is situated close to endocyclic nitrogen. All these calculations support our proposal that the vinyl proton is involved in intramolecular hydrogen bonding in 2-vinyloxy- and 2-vinylthiopyridines.Key words: NMR, intramolecular hydrogen bonding, ab initio calculation, GIAO.

Experimental and theoretical studies of the gas-phase protonation of vinyl ethers, vinyl sulfides, and vinyl selenides

1989 ◽  
Vol 111 (14) ◽  
pp. 5028-5036 ◽  
Author(s):  
K. Osapay ◽  
J. Delhalle ◽  
K. M. Nsunda ◽  
E. Rolli ◽  
R. Houriet ◽  
...  
Keyword(s):  
Gas Phase ◽  
Theoretical Studies ◽  
Vinyl Ethers ◽  
Vinyl Sulfides ◽  
Experimental And Theoretical Studies

Infrared spectroscopic determination of the basicity of vinyl ethers and vinyl sulfides

1970 ◽  
Vol 13 (1) ◽  
pp. 983-985
Author(s):  
N. I. Shergina ◽  
�. I. Kositsyna ◽  
A. S. Atavin ◽  
A. V. Gusarov ◽  
B. A. Trofimov
Keyword(s):  
Spectroscopic Determination ◽  
Vinyl Ethers ◽  
Vinyl Sulfides ◽  
Infrared Spectroscopic
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