Theoretical studies of rotational barriers of heteroatom derivatives of methanol

Journal Article · Thu Jun 14 04:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100375a020· OSTI ID:6190080

Wu, Yundong; Houk, K N ^[1]

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1. Univ. of California, Los Angeles (USA)

The rotational barrier about the C-O bond of methanol is well-known to be 1 kcal/mol. In this paper, the rotational barriers of heteroatom derivatives of methanol, CH{sub 3}OX, where X = F, Cl, O{sup {minus}}, OH, and OH{sub 2}{sup +}, are predicted to have the considerably higher values of 3.7, 3.5, 4.3, 3.3, and 3.5 kcal/mol, respectively, at the MP4/6-31G{sup **} basis set level, with staggered conformers being favored. These conformational preferences and rotational barriers are rationalized by a combination of antiperiplanar {sigma}{sub CH}-{sigma}{sup *}{sub OX} delocalization and {pi}-type orbital interactions between {pi}{sup *}{sub CH{sub 3}} and {pi}{sub -O-X} orbitals, both of which are maximized in the staggered conformation.

• OSTI ID: 6190080
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:12; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
CALCULATION METHODS
CONFORMATIONAL CHANGES
DATA ANALYSIS
ELEMENTS
ENERGY LEVELS
EXCITED STATES
HALOGENS
HYDROXY COMPOUNDS
MATHEMATICAL MODELS
METHANOL
NONMETALS
ORGANIC COMPOUNDS
ROTATIONAL STATES