Raman Optical Activity in the Skeletal Motions of (+)-(3R)-Methylcyclohexanone. Chiral Mixing of Inherently Achiral Vibrations

Teresa B. Freedman; James Kallmerten; Carl G. Zimba; William M. Zuk; Laurence A. Nafie

doi:10.1021/ja00317a013

Raman Optical Activity in the Skeletal Motions of (+)-(3R)-Methylcyclohexanone. Chiral Mixing of Inherently Achiral Vibrations

Teresa B. Freedman, James Kallmerten, Carl G. Zimba, William M. Zuk, Laurence A. Nafie

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The Raman and Raman optical activity (ROA) spectra of (+)-(3R)-methylcyclohexanone in the 100–650-cm^-1 region are assigned to 11 skeletal motions based on Raman studies and normal coordinate analysis of the parent compound and five specifically deuterated isotopomers. The origin of the three prominent bisignate ROA couplets observed in this region is explained in terms of chiral vibrational perturbation due to the presence of the methyl group which mixes the inherently achiral A′and A¹¹ skeletal modes of cyclohexanone. Molecular orbital intensity calculations using the Raman atomic polar tensor model for ROA show good agreement with experiment for the skeletal vibrations.

Original language	English (US)
Pages (from-to)	1244-1252
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	106
Issue number	5
DOIs	https://doi.org/10.1021/ja00317a013
State	Published - Feb 1 1984

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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abstract = "The Raman and Raman optical activity (ROA) spectra of (+)-(3R)-methylcyclohexanone in the 100–650-cm-1 region are assigned to 11 skeletal motions based on Raman studies and normal coordinate analysis of the parent compound and five specifically deuterated isotopomers. The origin of the three prominent bisignate ROA couplets observed in this region is explained in terms of chiral vibrational perturbation due to the presence of the methyl group which mixes the inherently achiral A′and A11 skeletal modes of cyclohexanone. Molecular orbital intensity calculations using the Raman atomic polar tensor model for ROA show good agreement with experiment for the skeletal vibrations.",

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T1 - Raman Optical Activity in the Skeletal Motions of (+)-(3R)-Methylcyclohexanone. Chiral Mixing of Inherently Achiral Vibrations

AU - Freedman, Teresa B.

AU - Kallmerten, James

AU - Zimba, Carl G.

AU - Zuk, William M.

AU - Nafie, Laurence A.

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N2 - The Raman and Raman optical activity (ROA) spectra of (+)-(3R)-methylcyclohexanone in the 100–650-cm-1 region are assigned to 11 skeletal motions based on Raman studies and normal coordinate analysis of the parent compound and five specifically deuterated isotopomers. The origin of the three prominent bisignate ROA couplets observed in this region is explained in terms of chiral vibrational perturbation due to the presence of the methyl group which mixes the inherently achiral A′and A11 skeletal modes of cyclohexanone. Molecular orbital intensity calculations using the Raman atomic polar tensor model for ROA show good agreement with experiment for the skeletal vibrations.

AB - The Raman and Raman optical activity (ROA) spectra of (+)-(3R)-methylcyclohexanone in the 100–650-cm-1 region are assigned to 11 skeletal motions based on Raman studies and normal coordinate analysis of the parent compound and five specifically deuterated isotopomers. The origin of the three prominent bisignate ROA couplets observed in this region is explained in terms of chiral vibrational perturbation due to the presence of the methyl group which mixes the inherently achiral A′and A11 skeletal modes of cyclohexanone. Molecular orbital intensity calculations using the Raman atomic polar tensor model for ROA show good agreement with experiment for the skeletal vibrations.

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Raman Optical Activity in the Skeletal Motions of (+)-(3R)-Methylcyclohexanone. Chiral Mixing of Inherently Achiral Vibrations

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