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A Versatile Synthetic Approach to Rhodium(III) Diimine Metallointercalators:  Condensation of o-Quinones with Coordinated cis-Ammines

Mürner, Hansruedi and Jackson, Brian A. and Barton, Jacqueline K. (1998) A Versatile Synthetic Approach to Rhodium(III) Diimine Metallointercalators:  Condensation of o-Quinones with Coordinated cis-Ammines. Inorganic Chemistry, 37 (12). pp. 3007-3012. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180524-164125514

[img] PDF (CD spectra of the enantiomers of [Rh(phen)_2(NH_3)_2]Cl_3 and [Rh(bpy)_2(chrysi)]Cl_3 and HPLC traces depicting the progress of the condensation of 9,10-phenanthrenequinone with [Rh(phen)(NH_3)_4]^(3+) and Δ-[Rh(phen)_2(NH_3)_2], respectively (4 pages)) - Supplemental Material
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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ic9800738DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic9800738PublisherSupporting Information
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
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.
Funders:
Funding AgencyGrant Number
NIHGM 33309
NSF Predoctoral FellowshipUNSPECIFIED
Swiss National Science Foundation (SNSF)UNSPECIFIED
Ciba-Geigy Jubilee FoundationUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20180524-164125514
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180524-164125514
Official Citation:A Versatile Synthetic Approach to Rhodium(III) Diimine Metallointercalators:  Condensation of o-Quinones with Coordinated cis-Ammines Hansruedi Mürner, Brian A. Jackson, and Jacqueline K. Barton Inorganic Chemistry 1998 37 (12), 3007-3012 DOI: 10.1021/ic9800738
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86611
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2018 14:34
Last Modified:03 Oct 2019 19:45

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