Ligands technetium complexes

Structural Characterization of Ternary Ligand Technetium Complexes. . . 142... 

Fig. 12 Possible structures for the ternary ligand technetium complex [99mTc(HYPY)-(tricine)(PPh3)]...

Le Bideau F, Salmain M, Top S et al (2001) New and efficient routes to biomolecules substituted with cyclopentadienyltricarbonylrhenium and -technetium derivatives. Chem Eur J 7 2289-2294 Leon A, Rey A, Mallo L et al (2002) Novel mixed ligand technetium complexes as 5-HTia receptor... 

The only technetium complex has been reported (226) is [Tc(CO)4(R2dtc)]. There appear to be few reports of rhenium or technetium complexes with 1,1-dithiolato ligands. 

The inability of amines to deprotonate upon coordination, and thus to compensate the charge of the MOs+ core, can be overcome by combination with other types of donors-including N-donor groups-in the ligand, as has already been discussed above for oxocyclam. A prominent example is provided by technetium complexes of tetradentate amine oxime ligands. 

Technetium complexes with thioethers in the strict sense, i.e., those without other donor groups in the ligand molecule, comprise homoleptic thioether nitridotechnetium(V) complexes [111], cationic mixed thioether/thiolate complexes of Tc(III) [112], and a cationic Tc(I) complex [113]. However, these latter compounds do not properly fall within the scope of Tc(V) compounds and are excluded from review. 

Another type of mixed ligand technetium or rhenium complexes in the above sense contains two or more monodentate ligands (Fig. 26b). The six-coordinated polypyridyl-thiolato complexes of rhenium(V) [ReO(terpy)(SR)2] + [186] are an example. Further representatives are a variety of mixed-ligand complexes, combining tetramethylthiourea with dimethyldithiocarbamate [TcO(tu)2-((CH3)2NCSS)]2+ [194],... 

Fig. 4. Schematic presentation of nearest ligand surrounding the binuclear d3-d3 and d3-d2 technetium complexes (according to [11])...

Literature data are available on the electronic structures of two more binuclear technetium complexes [(NHjLlOHLTcf/i-O TcfOH NHj ] (a hypothetical complex with the structure and composition analogous to those of the ethylen-diamminetetra-acetate complex [54,55]) and Tc2(CO)10 (a binuclear complex with strong crystal field ligands [168,169]. We shall consider the results of these calculations in greater detail. 

Technetium is usually supplied in the form of heptavalent pertechnetate. Consequently, the syntheses of technetium complexes is necessarily accompanied by the reduction of pertechnetate. When concentrated hydrochloric acid is employed as a reductant, tetrachlorooxotechnetate(V) complexes can easily be obtained. A further reduction procedure is required to obtain hexachlorotech-netate(IV). Using these complexes, a number of technetium complexes have been synthesized by ligand substitution. The importance of preparative substitution reactions also increases in the light of the design and preparation of radiopharmaceuticals labelled with 99mTc and 188Re. 

The most fundamental approach to assessing lability of complexes is by determination of the rate of isotopic exchange reactions. In the technetium-complex systems, no study of the exchange reaction on the central metal ion has been reported, but several reports have been published on isotopic exchange by ligand substitution. 

The reduction of pertechnetate with concentrated hydrochloric acid finally yields the tetravalent state, and no further reduction to the tervalent state takes place. Therefore, the tervalent technetium complex has usually been synthesized by the reduction of pertechnetate with an appropriate reductant in the presence of the desired ligand. Recently, the synthesis of tervalent technetium complexes with a new starting complex, hexakis(thiourea)technetium(III) chloride or chloropentakis(thiourea)technetium(III) chloride, has been developed. Thus, tris(P-diketonato)technetium(III) complexes (P-diketone acetylacetone, benzoyl-acetone, and 2-thenoyltrifluoroacetone) were synthesized by the ligand substitution reaction on refluxing [TcCl(tu)5]Cl2 with the desired P-diketone in methanol [28]. 

Investigation of the coordination of tetradentate N2S2 ligands has been reported for gallium and indium.79 This type of chelate had previously been incorporated into many technetium complexes for biomedical applications. 

Maecke, H. R. Eisenhut, M. Technetium complexes as radiopharmaceuticals. In Metal-Ligand Interactions in Biological Fluids, Berthon, G., Ed., Dekker New York, 1995. 

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