Technetium 1 complexes

Certain neutral technetium complexes can be used to image cerebral perfusion (Fig. 4). Those in Figure 4a and 4b have been approved for clinical use. Two other complexes (Fig. 4c and 4d) were tested in early clinical trials, but were not developed further. An effective cerebral perfusion agent must first cross the blood brain barrier and then be retained for the period necessary for image acquisition. Tc-bicisate is retained owing to a stereospecific hydrolysis in brain tissue of one of the ester groups to form the anionic complex TcO(ECD) , which does not cross the barrier. This mechanism of retention is termed metaboHc trapping. 

Several hydrophilic, anionic technetium complexes can be used to perform imaging studies of the kidneys. Tc-Mertiatide (Fig. 5a) is rapidly excreted by active tubular secretion, the rate of which is a measure of kidney function. Tc-succimer (Fig. 5b), on the other hand, accumulates in kidney tissue thus providing an image of kidney morphology. 

Blomstrand-Jorgensen chain theory, 1, 6 Blood coagulation calcium, 6,591 Blood/brain barrier brain imaging techniques technetium complexes, 6, 991 technetium complexes, 6,985 Blood plasma... 

Formamidine, N,N -di-2-anthraquinonyI-metal complexes, 2,275 Formamidine, IV.AT-diaryl-metal complexes, 2, 275 Formamidine, N, N -dibenzyl-metal complexes, 2,276 Formamidine, IV.N -diisopropyl-metal complexes, 2, 276 Formamidinesulfinic acid technetium complexes, 6, 974 Formate dehydrogenases bacteria... 

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. 

Technetium isotopes also help tremendously in the diagnosis of breast cancer. A technetium complex preferentially binds to cancer cells, so if a patient has cancer, radioactivity imaging will reveal high levels of radioactivity from the cancerous tissues. The red spot in the image below marks the location of cancerous cells. 

Ajayaghosh A, George SJ, Schenning APHJ (2005) Hydrogen-Bonded Assemblies of Dyes and Extended jr-Conjugated Systems. 258 83-118 Akai S, Kita Y (2007) Recent Advances in Pummerer Reactions. 274-. 35-76 Albert M, Fensterbank L, l.acote E, Malacria M (2006) Tandem Radical Reactions. 264 1-62 Alberto R (2005) New Organometallic Technetium Complexes for Radiopharmaceutical Imaging. 252 1-44... 

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... 

The tracer level Tc,nHA complex can be suspended as a colloid in an aqueous solution. Spedation of a similar complex, Am111 HA, in the Gorleben groundwater was performed by laser photoacoustic spectroscopy (LPAS) [33]. Considering its molecular size, however, migration of the complex is expected to be very slow when it is present in a solid phase. Similar LPAS studies of a technetium complex towards chemical spedation have been tried by our group in Sendai [36,37]. 

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. 

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. 

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). 

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. 

Tc2[(CH3)3CCOO]4 C12. The first binuclear d4-d4 technetium complex was obtained by Cotton and Gage [45] by oxidative substitution of the chloride ions in the coordination sphere of [Tc2Cl8]3 by trimethylacetate ions. The substitu-... 

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

From the results presented it follows that the driving force behind the growth of technetium clusters in the process of their reduction is a decrease in the total electron energy of the ions due to the formation of M-M bonds. In fact, as is shown in Fig. 6, if the M-M bonds were absent the total electron energy of technetium complexes would be considerably higher and the complex would be unstable. However, besides purely thermodynamic reasons leading to the cluster formation, there should also be kinetic possibilities for these processes to take place. This aspect of technetium cluster formation is partially considered below. 

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. 

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