Technetium complexes, structural

Acknowledging the important part that 99mTc(V) radiopharmaceuticals are playing in nuclear medicine, advances in their coordination chemistry, as attained by new syntheses and better structural characterization, are discussed with respect to the design of Tc(V) radiotracers. In the light of current interest in making technetium complexes active in vivo, a chapter considering several aspects of reactivity is included. 

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. 

Electronic Structure of Binuclear Technetium Complexes 5.2.1 Octachloroditechnetates... 

Calculations of the electronic structure of the complexes of this type were first carried out for [Tc2C18]3, using the semi-empirical EHT method [146], It was shown that a strong quadruple M-M bond is formed in both the d4-d4 binuclear transition-metal complexes and d4-d5 technetium complexes. The addition of an excess electron does not decrease the Tc-Tc bond strength,... 

Thus, the investigations performed [58,77] showed that [Tc2(/t-CH3COO)4] [TCO4J2 combines the properties of two classes of technetium complexes those of pertechnetates and those of binuclear carboxylates with multiple M-M bonds. On the other hand, the anionic and cationic fragments of this compound are characterized by a mutual effect which affects their electronic and molecular structures. 

However, X-ray diffraction data show [68,69] that in K2[Tc2C16], the Tc-Tc bond distance is 0.1 A shorter than that in an analogous d4-d4 chloride technetium complex, although its main structural fragment [Tc2C18]4- has a staggered structural conformation. That is why a study of the electronic... 

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. 

Metal-essential radiopharmaceuticals are those whose targeting properties are inherent in the structure and chemistry of the complex itself rather than a biomolecule whose targeting ability is independent of the attachment of the metal. While this class of tracers includes many well-developed technetium complexes, it includes relatively few rhenium complexes. 

The unique seven-coordinate complex [TcO(EDTA)] is obtained by reaction of [TcOCy with H4EDTA in anhydrous dmso. The X-ray crystal structure confirmed pentagonal-bipyrami-dal geometry, with the 0x0 group and the two nitrogen donors bound in the equatorial plane. " All other structurally characterized technetium complexes with polyamino-polycarboxylates are in oxidation state IV. 

Complexes of technetium in oxidation states ranging from (-1) to (VII) have been prepared chemically and characterized. However, historically only the higher oxidation states (IV), (V) and (VII) have been of major importance in radiopharmaceutical formulations. More recently there has been increased interest in lower oxidation state technetium complexes for medical applications, and the use of ir-acceptor ligands has allowed the preparation of Tc1 complexes which are stable in vivo. The coordination chemistry of technetium has been described in Chapter 42 and recent reviews have been provided by Davison21 and by Schwochau.22 Reviews which relate to medical applications of technetium are given by Jones and Davison,549 Deutsch et al.,20 Deutsch and Barnett,550 Siedel551 and Clarke and Fackler.552 The in vivo chemistry of "mTc chelates has been described by Eckelman and Volkert,553 while the structures of technetium complexes, determined by X-ray diffraction techniques, have been reviewed by Bandoli et ai554... 

Contents J.A.Ibers, L.J.Pace, J.Martinsen, B.M.Hoffman Stacked Metal Complexes Structures and Properties. -M.J. Clarke, P.H.Fackler The Chemistry of Technetium Toward Improved Diagnostic Agents. - R.J.P. Williams The Chemistry of Lanthanide Ions in Solution and in Biological Systems. - C.K. Jorgensen, R.Reisfeld Uranyl Photophysics. 

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

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