Technetium oxidation states

Table 4 presents the calculated results of the effective charges on technetium atoms in technetium compounds, arrived at by using various theoretical approximations. In technetium compounds with M-M bonds and formal technetium oxidation states 2.0 + and lower, Zeff is less than 1.0 +, whatever the... 

Technetium is a silvery-gray metal that tarnishes slowly in moist air. The common oxidation states of technetium are +7, +5, and +4. Under oxidizing conditions technetium (Vll) will exist as the pertechnetate ion, TcOr-. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and cone, sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. The metal is an excellent superconductor at IIK and below. 

Plutonium was the first element to be synthesized in weighable amounts (6,7). Technetium, discovered in 1937, was not isolated until 1946 and not named until 1947 (8). Since the discovery of plutonium in 1940, production has increased from submicrogram to metric ton quantities. Because of its great importance, more is known about plutonium and its chemistry than is known about many of the more common elements. The metallurgy and chemistry are complex. MetaUic plutonium exhibits seven aUotropic modifications. Five different oxidation states are known to exist in compounds and in solution. 

Table 24.3 Oxidation states and stereochemistries of manganese, technetium and rhenium...

The +4 Oxidation state ls the only uae in which all three elements form stable oxides, but only m the c.ase of technetium is this the most stable oxide. TcOz is the hnal product wi n any Tc/O... 

The chemistry of technetium(II) and rhenium(II) is meagre and mainly confined to arsine and phosphine complexes. The best known of these are [MCl2(diars)2], obtained by reduction with hypophosphite and Sn respectively from the corresponding Tc and Re complexes, and in which the low oxidation state is presumably stabilized by n donation to the ligands. This oxidation state, however, is really best typified by manganese for which it is the most thoroughly studied and, in aqueous solution, by far the most... 

The O-donor complexes of Tc(V) exhibit moderate and differential stability in aqueous solution. In the presence of reducing agents, such as stannous chloride, they are reduced to mainly undefined products of Tc in a lower oxidation state. However, at the low technetium concentration of "mTc that is used in nuclear medicine, the rate of the reduction process is very low. This makes it possible to prepare Tc(V) radiopharmaceuticals with O-donor ligands by the usual procedure, in which an excess of reducing agent over technetium is unavoidably used. The Tc(V) complexes also tend either to be easily oxidized or to disproportionate [23],... 

N-donor groups in the form of e-amino groups of lysine as nonspecific binding sites for technetium may play an undesired role in Tc-labelling of monoclonal antibodies for tumour imaging [51]. Nonspecifically bound Tc has a poor in vivo stability and appears to increase the undesired liver uptake and reduces tumour uptake. The metal oxidation state and coordination is not yet known. 

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. 

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