Technetium, synthesis

Saladino R, Crestini C, Costanzo G, DiMauro E (2005) On the Prebiotic Synthesis of Nucle-obases, Nucleotides, Oligonucleotides, Pre-RNA and Pre-DNA Molecules. 259 29-68 Santos I, Paulo A, Correia JDG (2005) Rhenium and Technetium Complexes Anchored by Phosphines and Scorpionates for Radiopharmaceutical Applications. 252 45-84 Santos M, see Szathmdry E (2005) 259 167-211... 

Complexation studies with bidentate phosphine ligands showed that stable cationic complexes of Tc(V), Tc(III), and Tc(I) are easily accessible. The influence of reaction conditions on reaction route and products is well demonstrated by the reaction of pertechnetate with the prototype 1,2-bis(dimethylphosphino)-ethane (dmpe) (Fig. 16). Careful control of reduction conditions allows the synthesis of [Tc02(dmpe)2]+, [TCl2(dmpe)2]+, and [Tc(dmpe)3]+, with the metal in the oxidation states V, III, and I [120,121]. This series illustrates the variety of oxidation states available to technetium and their successive generation by the action of a 2-electron reducing agent. 

The most convenient route to organometallic technetium complexes is directly from 3, under reaction conditions which allow working in a normal laboratory. There are basically three essential compounds that fulfil these conditions and can be prepared in a one step synthesis starting from 3, and which are convenient precursors for subsequent chemistry due to their reactivity (Scheme 1). 

To transfer the original synthesis to technetium was not very convenient, as it would have to start from TcBr(CO)5 (32a). A preparation has recently been reported which starts from 3a or 19a in refluxing THF and used BH3 as the reducing agent [36]. The complex 31a could be isolated in 60-70% yield, based on Tc, and has been characterized by i.r. specroseopic methods as well as Tc and Cl analysis, and compared to its rhenium congener (Scheme 5). 

Scheme 17. Synthesis of mixed oxo-alkyi complexes of high valency technetium and rhenium...

With autoclave syntheses a high yield of clusters is achieved, and it is possible for researchers to follow the reaction path in solution by gradually changing (from experiment to experiment) the working parameters of the synthesis (temperature, pressure, exposure at working temperatures, etc). All these advantages of the autoclave technique have resulted in an abundance of new forms of technetium clusters (particularly, polynuclear ones) because it has been possible to develop and improve the method of obtaining these compounds. 

Among other widely used reducers for the synthesis of binuclear technetium complexes with M-M bonds, zinc in HC1 and H3P02 [1,11] are most important. These reducers, as a rule, are used for the synthesis of Re clusters of similar structure. 

The specific features of the cluster compounds of technetium are such, that practically each new compound must be studied using single crystal X-ray structural analysis, because their complex structures do not allow the interpretation of the results from other physico-chemical methods of investigation. Therefore, the synthesis of single crystals suitable for X-ray structural analysis is the main and most laborious chemical task. 

The first communications about the synthesis [9,49] and structure [9,70,101] of polynuclear technetium halides appeared in 1982-83. These studies demonstrated the superior capacity of technetium to form polynuclear... 

Thus partial evaporation of HC1 during the synthesis of [Tc2C18]3 by the method of Eakins et al. [24] and by the autoclave method [22,42,43] creates favorable conditions (from the standpoint of the acidity of the solution and the concentration of technetium ions in it) for the formation of the octachloro-ditechnetates (+2.5), since, on the one hand, the rate of reduction of the technetium(IV) ions increases owing to their hydrolysis [42] and, on the other hand, the stability of the hydrolyzed cluster ions formed increases in relation to the reactions involving disproportionation and oxidation by atmospheric oxygen [9,52,80,87]. We may note that under the conditions of more pronounced hydrolysis, the rate of reduction of technetium(IV) increases so much that the formation of metallic technetium becomes possible. 

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]. 

Crystals of [Tc(tu)6]Cl3 or [TcCl(tu)5]Cl2 are often employed for the synthesis of technetium(III) complexes. However, since the direct reduction of pertechnetate with excess thiourea in a hydrochloric acid solution yields [Tc(tu)6]3+ in high yield [37], direct use of the aqueous solution of the thiourea complex would be preferable for the synthesis of the technetium(III) complex without isolation of the crystals of the thiourea complex. In fact, technetium could be extracted from the aqueous solution of the Tc-thiourea complex with acetylacetone-benzene solution in two steps [38]. More than 95% extraction of technetium was attained using the following procedure [39] First a pertechnetate solution was added to a 0.5 M thiourea solution in 1 M hydrochloric acid. The solution turned red-orange as the Tc(III)-thiourea complex formed. Next, a benzene solution containing a suitable concentration of acetylacetone was added. After the mixture was shaken for a sufficient time (preliminary extraction), the pH of the aqueous phase was adjusted to 4.3 and the aqueous solution was shaken with a freshly prepared acetylacetonebenzene solution (main extraction). The extraction behavior of the technetium complex is shown in Fig. 6. The chemical species extracted into the organic phase seemed to differ from tris(acetylacetonato)technetium(III). Kinetic analysis of the two step extraction mechanism showed that the formation of 4,6-dimethylpyrimidine-... 

Another attempted synthesis of Tc(III)-EDTA and Tc(III)-HEDTA complexes (EDTA ethylenediaminetetraacetic acid HEDTA A -(2-hydroxy-methyl)ethylenediamine-N,AT, iV -triacetic acid) was carried out using [Tc(tu)6]3+ as the starting complex [40]. Technetium-EDTA complexes have been synthesized by the direct reduction of pertechnetate with a suitable reduc-tant in the presence of excess EDTA [41-43]. On addition of EDTA to the Tc(tu) + solution, the intensity of the absorption spectrum decreased with time and the solution color changed from reddish orange to light brown. An electrophoretic analysis for the Tc(III)-EDTA complex showed that more than 70%... 

Omori, T. Substitution Reactions of Technetium Compounds. 176, 253-274 (1996). Ostrowicky, A., Koepp, E., Vogtle, F. The Vesium Effect Synthesis of Medio- and Macrocyclic Compounds. 161, 37-68 (1991). 

M. Gottschaldt, D. Koth, D. Muller, I. Klette, S. Rau, H. Gorls, B. Schafer, R. P. Baum, and S. Yano, Synthesis and structure of novel sugar-substituted bipyridine complexes of rhenium and 99m-technetium, Chem. Eur. 13 (2007) 10273-10280. 

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