METAL-CARBONYL SYNTHESES .20. SIMPLE METHOD FOR THE PREPARATION OF TC(CO)3 COMPLEXES - SYNTHESIS, STRUCTURES, AND REACTIVITY OF THE NOVEL CUBANE-TYPE CLUSTER NA[TC3(CO)9(OCH3)4]

Carbonyltechnetium complexes of type LTc(CO)3 are accessible along a simple route from Na[Tc3(CO)9(OCH3)4] (2) which represents a novel alkoxy complex of cubane-type geometry (single-crystal X-ray diffraction study). 2 is an isolable product of the incomplete carbonylation of sodium pertechnetate (1) conducted in methanol. Under carbon monoxide pressure, 2 yields the binary metal carbonyl Tc2(CO)10 (3), pentamethylcyclopentadiene gives the halfsandwich complex (eta-5-C5Me5)Tc(CO)3 (4), and with benzene/hydrochloric acid the ionic complex [(eta-6-C6H6)Tc(CO)3]Cl (5) is formed.