Thioether technetium

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. 

Technetium compounds with amine/thioether coordination are the cationic trans-dioxotechnetium(V) complexes [Tc02(N2S2)]+. The complex in which N2S2 is l,4-dithia-8,ll-diazacyclotetradecane was prepared via an exchange reaction of NBu4[TcOBr4] with the ligand and fully characterized by X-ray crystal structure determination [109,110]. The coordination around technetium... 

An unusual reaction pattern has been found for the electrochemical and chemical (by ascorbic acid) reduction of the rhenium(II) thioether complex [Re(9S3)2] " (9S3 = 1,4,7-trithiacyclono-nane). Instead of the formation of the corresponding rhenium(I) complex, C bond cleavage and the release of ethene was observed and the brown rhenium(III) species [Re(9S3)(SC2H4SC2H4S)]" (250) was isolated as a BF4 salt. Lfpon electrochemical reduction of [Re(9S3)(SC2H4SC2H4S)]" further loss of ethene was observed while the analogous technetium complex can be reversibly reduced to [Tc(9S3)(SC2H4SC2H4S)]. 

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