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Pseudorotation : ウィキペディア英語版
Pseudorotation

A pseudorotation is a set of intramolecular movements of attached groups (i.e., ligands) on a highly symmetric molecule, leading to a molecule indistinguishable from the initial one. The International Union of Pure and Applied Chemistry (IUPAC) defines a pseudorotation as a "()tereoisomerization resulting in a structure that ''appears'' to have been produced by rotation of the entire initial molecule", the result of which is a "product" that is "superposable on the initial one" and there, unless different positions are distinguished by… isotopic labeling."〔Here and following, see IUPAC, 1997, "Compendium of Chemical Terminology," 2nd ed. (AD McNaught & A Wilkinson, compilers; the "Gold Book"), Oxford, UK: Blackwell Scientific Publications, ISBN 0-9678550-9-8, DOI:10.1351/goldbook, see (); online XML version (2006-) created by M Nic, J Jirat & B Kosata with updates by A Jenkins, accessed 28 May 2014.〕 Well known examples are the intramolecular isomerization of trigonal bipyramidal compounds by the Berry pseudorotation mechanism, and the out-of-plane motions of carbon atoms exhibited by cyclopentane, leading to the interconversions it experiences between its many possible conformers (envelope, twist). Note, no angular momentum is generated by this motion. In these and related examples, a small displacement of the atomic positions leads to a loss of symmetry until the symmetric product re-forms (see image example below), where these displacements are typically along low-energy pathways. The Berry mechanism refers to the facile interconversion of axial and equatorial ligand in MX5 types of compounds, e.g. D3h-symmetric PF5 (shown). Finally, in a formal sense, the term pseudo rotation is intended to refer exclusively to dynamics in symmetrical molecules, though mechanisms of the same type are invoked for lower symmetry molecules as well.

==References==


抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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