Synthesis and properties of new DNA cleavage agents based on oxoruthenium(IV)

Journal Article · Wed Feb 03 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00055a014· OSTI ID:6709307

Gupta, N; Grover, N; Neyhart, G A; Singh, P; Thorp, H H ^[1]

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1. North Carolina State Univ., Raleigh (United States)

New aquaruthenium(II) reagents that are capable of being oxidized to hydrooxoruthenium(III) and oxoruthenium(IV) have been prepared. Complexes based on Ru(tpy)(L)OH[sub 2][sup 2+] (L = [eta][sup 2]-tpt, phen, dppz, tmen; tpy = 2,2[prime]:6[prime],2[double prime]-terpyridine, tpt = 2,4,6-tripyridyltriazine, phen = 1,10-phenanthroline, dppz = dipyridophenazine, and tmen = N,N,N[prime],N[prime]-tetramethylethylenediamine) have been prepared and can all be reversibly oxidized to their Ru[sup IV]O forms, which are component DNA cleavage agents, as in Ru(phen)[sub 2](py)O[sup 2+]. In addition to Ru(tpy)([eta][sup 2]-tpt)OH[sub 2][sup 2+], the [eta][sup 3] complex of tpt, Ru(tpy)([eta][sup 3]-tpt)[sup 2+], can also be prepared under similar conditions. In the presence of Ag[sup +] ion, a novel Ru[sub 2]Ag complex can be isolated and has been crystallographically characterized. The complex [Ru(tpy)([eta][sup 3]-tpt)](ClO[sub 4])[sub 2][center dot]0.5AgClO[sub 4][center dot]0.5H[sub 2]O crystallizes in the monoclinic space group A2/A with a = 14.723 (5) [Angstrom], b = 26.061 (6) [Angstrom], c = 22.148 (6) [Angstrom], [beta] = 106.33 (3)[degrees], V = 8155 (5) [Angstrom][sup 3], Z = 4, R = 0.0807, and R[sub w] = 0.1156 for 2,923 reflections with I [ge] 2[sigma](I). The Ru(tpy)OH[sub 2][sup 2+] unit can also be attached to the tmen-AO[sup +] ligand, where a N,N[prime],N[prime]-trimethylethylenediamine function is appended via a (CH[sub 2])[sub 6] linker to the acridine orange intercalator. The Ru(tpy)(tmen-AO)OH[sub 2][sup 3+] complex is an effective cleavage agent, but only when oxidation is performed on the complex prebound to DNA. In homogeneous solution, electrochemically reversible access of only the Ru[sup III]OH form is possible, probably because of oxidation of the polymethylene linker. 25 refs., 11 figs., 9 tabs.

• OSTI ID: 6709307
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:3; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DNA
OXIDATION
RUTHENIUM COMPLEXES
CHEMICAL PREPARATION
RUTHENIUM HYDROXIDES
RUTHENIUM OXIDES
ACRIDINE ORANGE
CATIONS
CRYSTAL STRUCTURE
ELECTROCHEMISTRY
LATTICE PARAMETERS
LIGANDS
MONOCLINIC LATTICES
PHENANTHROLINES
X-RAY DIFFRACTION
ACRIDINES
AMINES
AROMATICS
AZAARENES
AZINES
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
DYES
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXIDES
IONS
NUCLEIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PYRIDINES
REFRACTORY METAL COMPOUNDS
RUTHENIUM COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties