A nuclear magnetic resonance calibration of ab initio and semiempirical molecular orbital calculations of the conformational energies of 2‐fluorobenzyl alcohol

1976 ◽  
Vol 65 (3) ◽  
pp. 1197-1201 ◽  
Author(s):  
Ted Schaefer ◽  
William J. E. Parr
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Ab Initio ◽  
Molecular Orbital ◽  
Molecular Orbital Calculations ◽  
Conformational Energies ◽  
Semiempirical Molecular Orbital ◽  
Nuclear Magnetic

1H nuclear magnetic resonance and molecular orbital studies of the conformations of 3-fluoroanisole

1989 ◽  
Vol 67 (6) ◽  
pp. 1027-1031 ◽  
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Molecular Orbital ◽  
Substituent Effects ◽  
Spin Coupling ◽  
Basis Set ◽  
Molecular Orbital Calculations ◽  
Minimal Basis ◽  
Parent Molecule ◽  
Nuclear Magnetic

The proximate spin–spin coupling constant between the methyl protons and the ring protons, 5J(H,OCH3), is extracted from a full analysis of the 1H and 19F nuclear magnetic resonance spectra of 3-fluoroanisole in CS2 and acetone-d6 solutions. The values of 5J(H,OCH3) imply that the less polar cis conformer is slightly more stable at 300 K than the more polar trans conformer in both solvents, in agreement with geometry-optimized STO-3G MO computations for the free molecule. The latter also find a higher barrier to internal rotation of the methoxy group for 3-fluoroanisole than for the parent molecule. The present results are compared with other measurements of the conformer ratio for the vapor and for solutions. The STO-3G and 6-31G structures of the cis and trans conformers are compared. The C—F bond length is computed more reliably with the minimal basis set, as is the COC bond angle. The internal angles of the benzene moiety are, of course, found more accurately with the 6-31G basis. The computations indicate additivity of the substituent effects on the internal angle, as found experimentally for a variety of benzene derivatives. Keywords: 1H NMR of fluoroanisole, conformations of fluoroanisole, molecular orbital calculations for fluoroanisole.

Molecular orbital calculations and 1H nuclear magnetic resonance spectra as indicators of internal rotational potentials in some methyl derivatives of styrene

1988 ◽  
Vol 66 (4) ◽  
pp. 584-590 ◽  
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian ◽  
Glenn H. Penner
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Molecular Orbital ◽  
Long Range ◽  
Coupling Constants ◽  
Molecular Orbital Calculations ◽  
Carbon Carbon Bond ◽  
Nuclear Magnetic Resonance Spectra ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The 1H nuclear magnetic resonance spectra of the α-methyl, cis and trans-β-methyl, 4-methyl, and β,β-dimethyl styrènes are analyzed to yield long-range proton–proton coupling constants. With the assumptin that the internal rotational potential for styrene in the gas phase is unaltered in solution, a consistent treatment of over 40 of the long-range coupling constants is given in terms of the known coupling mechanisms. Expectation values of sin2 θ, where θ is the angle of twist about the exocyclic carbon–carbon bond, are presented for these molecules. These are compared with theoretical potentials at the 6-31 G level of molecular orbital theory. The present data indicate rather larger average twist angles than those in the literature. The extrema (at θ = θ° and 90°) in the angle dependent long-range coupling constants appear to be rather smaller in magnitude than are theoretical values obtained from valence bond and molecular orbital approaches.

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