A Versatile Synthetic Approach to Rhodium(III) Diimine Metallointercalators: Condensation of o-Quinones with Coordinated cis-Ammines
Abstract
A new route to the preparation of rhodium(III) diimine complexes which bind DNA by intercalation was developed by condensation of coordinated ammine ligands with o-quinones. Starting from cis-[Rh(L∧L)_2(NH_3)_2]^(3+) (L∧L: 2,2'-bipyridine or 1,10-phenanthroline) and the appropriate quinones the ligands 9,10-phenanthrenequinone diimine (phi) and 5,6-chrysenequinone diimine (chrysi) were introduced in high yields. The reactions are completed within hours at ambient temperature in MeCN/water mixtures, 0.1 M in NaOH. Experiments with enantiomerically pure Δ-[Rh(phen)_2(NH_3)_2]^(3+) and 9,10-phenanthrenequinone showed that the configuration at the metal center is retained during the course of the reaction. Condensation of rhodium(III) tetraammine starting material with 9,10-phenanthrenequinone allows the selective introduction of one or two phi ligands, depending on the reaction conditions. The ability to incorporate specifically only one phi ligand makes this a promising approach for the synthesis of tris(heteroleptic) coordination compounds, and one example of such a complex, [Rh(phen)(phi)(chrysi)]^(3+), is provided.
Additional Information
© 1998 American Chemical Society. Received January 22, 1998. We are grateful to the National Institutes of Health (GM 33309) for their financial support. B.A.J. thanks the National Science Foundation for a predoctoral fellowship. H.M. gratefully acknowledges fellowships from the Swiss National Science Foundation and the Ciba-Geigy Jubilee Foundation. We thank P. Belser and A. von Zelewsky for kindly providing d8-2,2'-bipyridine and A. Sargeson for helpful discussions.Attached Files
Supplemental Material - ic3007.pdf
Files
Name | Size | Download all |
---|---|---|
md5:b38225add9ac3509787108f2717c1e37
|
201.8 kB | Preview Download |
Additional details
- Eprint ID
- 86611
- Resolver ID
- CaltechAUTHORS:20180524-164125514
- NIH
- GM 33309
- NSF Predoctoral Fellowship
- Swiss National Science Foundation (SNSF)
- Ciba-Geigy Jubilee Foundation
- Created
-
2018-05-25Created from EPrint's datestamp field
- Updated
-
2021-11-15Created from EPrint's last_modified field