Technetium(I) Carbonyl Chemistry with Small Inorganic Ligands.

[Tc(OH 2 )(CO) 3 (PPh 3 ) 2 ](BF 4 ) 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 4 - . The formation of bond isomers and/or a distinct reactivity has been observed for most of the products. [Tc(NCO)(CO) 3 (PPh 3 ) 2 ], [Tc(NCS)(CO) 3 (PPh 3 ) 2 ], [Tc(CN)(CO) 3 (PPh 3 ) 2 ], [Tc(N 3 )(CO) 3 (PPh 3 ) 2 ], [Tc(NCO)(OH 2 )(CO) 2 (PPh 3 ) 2 ], [Tc(η 2 -OON)(CO) 2 (PPh 3 ) 2 ], [Tc(η 1 -NO 2 )(CO) 3 (PPh 3 ) 2 ], [Tc(η 2 -OONO)(CO) 2 (PPh 3 ) 2 ], [Tc(η 1 -ONO 2 )(CO) 3 (PPh 3 ) 2 ], [Tc(η 2 -OO(CCH 3 ))(CO) 2 (PPh 3 ) 2 ], [Tc(η 2 -SSC(SCH 3 ))(CO) 2 (PPh 3 ) 2 ], [Tc(η 2 -SSC(OCH 3 ))(CO) 2 (PPh 3 ) 2 ], [Tc(η 2 -SSC(CH 3 ))(CO) 2 (PPh 3 ) 2 ], [Tc(η 2 -SS(CH))(CO) 2 (PPh 3 ) 2 ], [Tc(OTcO 3 )(acetone)(CO) 2 (PPh 3 ) 2 ], [Tc(OTcO 3 )(CO) 3 (PPh 3 ) 2 ], and [Tc(η 2 -HHBH 2 )(CO) 2 (PPh 3 ) 2 ] have been isolated in crystalline form and studied by X-ray crystallography. Additionally, the typical reactivity patterns (isomerization, thermal decomposition, hydrolysis, or decarbonylation) of the products have been studied by spectroscopic methods. 99 Tc NMR spectroscopy has proved to be a particularly useful tool for the evaluation of such reactions of the diamagnetic technetium(I) compounds in solution.