Pseudorotation

From Wikipedia, the free encyclopedia
Jump to navigation Jump to search

Template:Short description

In chemistry, 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 "stereoisomerization 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, unless different positions are distinguished by substitution, including isotopic substitution."[1]

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).[2] Note, no angular momentum is generated by this motion.Script error: No such module "Unsubst". 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.Script error: No such module "Unsubst". The Berry mechanism refers to the facile interconversion of axial and equatorial ligand in Template:Chem2 types of compounds, e.g. D3h-symmetric Template:Chem2 (shown).[1][3] Finally, in a formal sense, the term pseudorotation is intended to refer exclusively to dynamics in symmetrical molecules, though mechanisms of the same type are invoked for lower symmetry molecules as well.Script error: No such module "Unsubst".

Pseudorotation of Iron-Pentacarbonyl-Complex (Berry mechanism)
Pseudorotation of Iron-Pentacarbonyl-Complex (Berry mechanism)

See also

References

Template:Reflist


Template:Stereochemistry-stub

  1. a b Script error: No such module "citation/CS1".
  2. Script error: No such module "Citation/CS1".
  3. Script error: No such module "Citation/CS1".