Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands.

[Tc(OH)(CO)(PPh)](BF) has been used as a synthon for reactions with small inorganic ligands with relevance for the treatment of nuclear waste solutions such as nitrate, nitrite, pseudohalides, permetalates (M = Mn, Tc, Re), and BH. The formation of bond isomers and/or a distinct reactivity has been observed for most of the products. [Tc(NCO)(CO)(PPh)], [Tc(NCS)(CO)(PPh)], [Tc(CN)(CO)(PPh)], [Tc(N)(CO)(PPh)], [Tc(NCO)(OH)(CO)(PPh)], [Tc(η-OON)(CO)(PPh)], [Tc(η-NO)(CO)(PPh)], [Tc(η-OONO)(CO)(PPh)], [Tc(η-ONO)(CO)(PPh)], [Tc(η-OO(CCH))(CO)(PPh)], [Tc(η-SSC(SCH))(CO)(PPh)], [Tc(η-SSC(OCH))(CO)(PPh)], [Tc(η-SSC(CH))(CO)(PPh)], [Tc(η-SS(CH))(CO)(PPh)], [Tc(OTcO)(acetone)(CO)(PPh)], [Tc(OTcO)(CO)(PPh)], and [Tc(η-HHBH)(CO)(PPh)] have been isolated in crystalline form and studied by X-ray crystallography.