Vibrational circular dichroism and infrared spectra of 2-methyloxirane and trans-2,3-dimethyloxirane: ab initio vibronic coupling theory with the 6-31G*(0.3) basis set

1992 ◽  
Vol 96 (1) ◽  
pp. 437-446 ◽  
Author(s):  
Arvi Rauk ◽  
Danya Yang
Keyword(s):  
Circular Dichroism ◽  
Ab Initio ◽  
Infrared Spectra ◽  
Vibronic Coupling ◽  
Vibrational Circular Dichroism ◽  
Basis Set ◽  
Coupling Theory ◽  
Circular Dichroïsm

Electronic and Vibrational Circular Dichroism of Model β-Lactams: 3-Methyl- and 4-Methylazetidin-2-one

1996 ◽  
Vol 50 (5) ◽  
pp. 630-641 ◽  
Author(s):  
Jennifer McCann ◽  
Arvi Rauk ◽  
Gennadii V. Shustov ◽  
Hal Wieser ◽  
Danya Yang
Keyword(s):  
Circular Dichroism ◽  
Ab Initio ◽  
Electronic Transition ◽  
Vibrational Circular Dichroism ◽  
Protic Solvent ◽  
Free Energies ◽  
Chiroptical Properties ◽  
Circular Dichroïsm ◽  
Rotational Strengths ◽  
Simple Modeling

The chiroptical properties of the simplest chiral β-lactams, 3- and 4-methylazetidin-2-one, 1 and 2, respectively, were investigated. The experimental vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra were measured and compared with ab initio predictions. Both compounds were found to form dimers with calculated binding enthalpies and free energies of about −51 kJ/mol and −6 to −8 kJ/mol, respectively. The experimentally measured IR and VCD spectra were measured in concentrated nonpolar (CCl4) solution and are in agreement with the predicted IR and VCD spectra of the dimeric forms, 12 and 22, but not the monomers. The most intense dimer VCD bands originate from in-plane N-H wags, which perturb the H-bonded cyclic array. At the more dilute concentrations employed for the ECD spectra, the experimental ECD spectra in heptane were interpreted satisfactorily as arising from a mixture consisting predominantly of monomers. In protic solvent (H2O, MeOH), the ECD spectra are consistent with H-bonded monomers. Simple modeling suggests that the rotational strengths of the first electronic transition gain most of their intensity from the nonplanarity of the amide chromophore, the contributions of which follow a spiral rule previously enunciated.

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