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DNA as a Catalyst and Catalytic Template for the Racemisation of Metal Tris‐Phenanthroline Complexes
Author(s) -
Rodger Alison,
Nordén Bengt,
Rodger P. Mark,
Bates Paula J.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20021)2002:1<49::aid-ejic49>3.0.co;2-8
Subject(s) - phenanthroline , chemistry , catalysis , enantiomer , dna , stereochemistry , metal , cobalt , crystallography , combinatorial chemistry , organic chemistry , biochemistry
[Fe(1,10‐phenanthroline) 3 ] 2+ is known to racemise in solution and DNA is known to shift the equilibrium point of the Δ/Λ‐[Fe(1,10‐phenanthroline) 3 ] 2+ mixture from 50:50 to a position favouring a slight excess of the Δ enantiomer. In this paper it is shown that DNA catalyses the racemisation reaction, presumably by providing vibrational energy to species that bind in a less favoured mode for that enantiomer. The racemisation of [Co(1,10‐phenanthroline) 3 ] 3+ , however, is not enhanced by DNA unless [Co(1,10‐phenanthroline) 3 ] 2+ is also added to the solution. In this case, the DNA acts as a template to facilitate the Co II ↔ Co III electron transfer. Racemisation occurs while the [Co(1,10‐phenanthroline) 3 ] n+ is in the labile Co II form.