Mono, bis or tris(substituted 2,2'-bipyridine) iron, ruthenium,

Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing

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556 42, 556 43, 556 44, 556138, 556140, 556146, 10628718, C07F 1500, C07F 1502, C07F 1900, C09K 300

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053939034

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BRIEF SUMMARY
TECHNICAL FIELD

The instant invention relates to a new family of mono, bis or tris(substituted 2,2'-bipyridine) iron, ruthenium, osmium or vanadium complexes, the bipyridine being substituted by at least one electron donor group. This invention also relates to methods for the preparation of these complexes.


BACKGROUND OF THE INVENTION

Determination of the concentration of certain components, especially glucose in biological fluids, has been considerably improved by the use of amperometric sensors using an electrode coated with a mediator and with an enzyme specific to said component, for example glucose oxidase, for the detection of glucose. These sensors thus make it possible to measure the transfer of electrons passing between the enzyme and the electrode by the intermediary of the mediator, this electron transfer being proportional to the amount-of component present in the sample of the biological fluid to be tested.
The quality of these sensors, i.e., their accuracy, the reproducibility of the results given by several sensors of the same series, their reliability and the speed of their response time largely depends upon the mediator used.
Mediators known to date, for example from U.S. Pat. No. 4,545,382 of Genetics International, include polyviologen, chloranil, fluoranil or ferrocene.
These mediators have, however, a certain number of disadvantages.
Because they do not transfer the electrons between the enzyme and the electrode sufficiently quickly, the response time of the sensor is rather long. In addition, some of these mediators, such as ferrocene, are relatively volatile or unstable, particularly when exposed to light and the sensors have to be stored under rather strict lighting and temperature conditions. In addition some mediators, especially ferrocene, decompose in water by hydrolysis which is a disadvantage when the sensors are used in blood.
Finally, oxygen enters into competition with some of these mediators and the results of glucose concentration measurements vary according to the amount of oxygen present in the blood. This can be a disadvantage depending on whether venous or arterial blood is being examined.


DISCLOSURE OF THE INVENTION

It was consequently desirable to seek and prepare mediators that are fast, stable and do not have interference problems with oxygen.
This search for mediators has led to the preparation of a new family of mono, bis or tris(substituted 2,2'-bipyridine) complexes of iron, ruthenium, osmium or vanadium, the bipyridine being substituted by at least one electron donor group.
This new family of complexes is not only of theoretical interest, but also above all because of these good mediator properties and the many other practical applications which it could have.
The invention will be better understood from a study of the following description of the family of complexes and of various embodiments of the processes for preparing these complexes.
The new family of mono, bis or tris(substituted 2,2'-bipyridine) complexes of a metal M has the following general formula (I): ##STR1## in which M is iron, osmium, ruthenium or vanadium.
L represents a bipyridine substituted by at least one electron donor group, conferring on the complex the oxidation-reduction properties desirable for a mediator.
A preferred complex of the metal M has the following general formula (I): ##STR2## in which R and R' are the same and each is a hydroxy, alkoxy or aryloxy group or a primary, secondary or tertiary amine group.
L.sub.1, L.sub.2, L.sub.3, L.sub.4 are ligands forming a coordination complex with iron, osmium, ruthenium or vanadium.
It will also be noted that in these complexes, the ligand L preferably represents a bipyridine disubstituted in the 4,4'-positions and more particularly 4,4'-dihydroxy-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine or 4,4'-bis(N,N-ethyl amino)-2,2'-bipyridine also known as 4,4'-bis(N,N -diethylamino)-2,2'-bipyridine, the complexes then having the following general formulae referenced (II), (III) and (IV) respectively: ##STR3##
The ligands L.sub.1,

REFERENCES:
patent: 4545382 (1985-10-01), Higgins et al.
patent: 4745076 (1988-05-01), Muller et al.
patent: 5075447 (1991-12-01), Muller et al.
GB, A, 95642 (The Australian National University) 22 Apr. 1984.
Organic Magnetic Resonance, vol. 22, No. 6, Jun. 1984, M. J. Cook et al.: "Luminescent metal complexes 4+-13C NMR spectra of the tris chelates of substituted 2,2'-bipyridyls and 1,10-phenanthrolines with ruthenium(II) and osmium(II)", pp. 388-394.
Chemical Abstracts, vol. 113, 1990, (Columbus, Ohio, US), L. Della Ciana et al.: "Synthesis and characterzation of a new family of luminescent cis-(4,4'-X2-5,5'-Y2-2,2'-bipyridine)20s(CO)CI(PF6) complexes (X=NEt2, OMe, Me, H, CL, Y=H; X=H, Y=Me; X=Y=Me): control of excited-state properties by bipridyl substituents", p. 814, No. 90292a, & INORG. CHEM. 1990, 29(15), 2792-8.
Chemical Abstracts, vol. 101, 1984, (Columbus, Ohio, US), K. J. Takeuchi et al.: "Redox and spectral properties of monooxo polypyridyl complexes of ruthenium and osmium in aqueous media", p. 574, No. 16171w, & INORG. CHEM. 1984, 23(13), 1845-51.
Journal of the Chemical Society Perkin Transactions II, vol. 8, 1984, M. J. Cook et al.: "Luminescent metal complexes. Part 1. Tris-chelates of substituted 2,2'-bipyridyls with ruthenium(II) as dyes for luminescent solar collectors", pp. 1293-1301.
Journal of the Chemical Society Perkin Transactions II, vol. 8, 1984, M. J. Cook et al.: "Luminescent metal complexes. Part 2. A model for the luminescence properties of the tris-chelates of substituted 2,2'-bipyridyls with ruthenium (II)", pp. 1303-1307, see the whole article.
Chemical Abstracts, vol. 100, 1984, (Columbus, Ohio (US), E. C. Constable: "Nucleophilic attack upon coordinated heterocycles definitive evidence for the enhanced electrophilicity of coordinated pyridines", see p. 701, abstract No. 150011b, & INORG. CHIM. ACTA 1984, 82(1), 53-7, see the whole article.
Journal of the Chemical Society, Chemical Communications, No. 13, 1988, M. K. Nazeerudin et al.: "Spontaneous oxidation of water to oxygen by the mixed-valence mu-oxo ruthenium dimer L2(H20)RuIII-O-RuIV(OH)L2 (L=2,2'-bipyridyl-5,5'-dicarboxylic acid)", pp. 872-874, see the whole article.
Gopinathan et al., Indian Journal of Chemistry. vol. 25A, Nov. 1986, pp. 1015-1017.
Araki et al., Bull. Chem. Soc. Japan. 63(5), 1990, pp. 1299-1304.

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