We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
X‐ray Crystal Structures Show DNA Stacking Advantage of Terminal Nitrile Substitution in Ru‐dppz Complexes.
- Authors
McQuaid, Kane; Hall, James P.; Brazier, John A.; Cardin, David J.; Cardin, Christine J.
- Abstract
The new complexes [Ru(TAP)2(11‐CN‐dppz)]2+, [Ru(TAP)2(11‐Br‐dppz)]2+and [Ru(TAP)2(11,12‐diCN‐dppz)]2+ are reported. The addition of nitrile substituents to the dppz ligand of the DNA photo‐oxidising complex [Ru(TAP)2(dppz)]2+ promote π‐stacking interactions and ordered binding to DNA, as shown by X‐ray crystallography. The structure of Λ‐[Ru(TAP)2(11‐CN‐dppz)]2+ with the DNA duplex d(TCGGCGCCGA)2 shows, for the first time with this class of complex, a closed intercalation cavity with an AT base pair at the terminus. The structure obtained is compared to that formed with the 11‐Br and 11,12‐dinitrile derivatives, highlighting the stabilization of syn guanine by this enantiomer when the terminal base pair is GC. In contrast the AT base pair has the normal Watson–Crick orientation, highlighting the difference in charge distribution between the two purine bases and the complementarity of the dppz–purine interaction. The asymmetry of the cavity highlights the importance of the purine–dppz–purine stacking interaction. Ligand stacking: Addition of one or two terminal nitrile groups to the dppz ligand improves the stacking capability of the ligand, shown by the formation of a closed intercalation cavity.
- Subjects
X-ray crystallography; CRYSTAL structure; NITRILE derivatives; SUBSTITUTION reactions; SUBSTITUENTS (Chemistry)
- Publication
Chemistry - A European Journal, 2018, Vol 24, Issue 59, p15859
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201803021