Theoretical studies of rotational barriers of heteroatom derivatives of methanol

Journal Article · Thu Jun 14 00:00:00 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), Vol. 94:12; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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