REACTIONS WITH THE TECHNETIUM AND RHENIUM CARBONYL-COMPLEXES (NET(4))(2)[MX(3)(CO)(3)] - SYNTHESIS AND STRUCTURE OF [TC(CN-BU(T))(3)(CO)(3)](NO3) AND (NET(4))[TC-2(MU-SCH2CH2OH)(3)(CO)(6)]
R. Alberto et al., REACTIONS WITH THE TECHNETIUM AND RHENIUM CARBONYL-COMPLEXES (NET(4))(2)[MX(3)(CO)(3)] - SYNTHESIS AND STRUCTURE OF [TC(CN-BU(T))(3)(CO)(3)](NO3) AND (NET(4))[TC-2(MU-SCH2CH2OH)(3)(CO)(6)], Polyhedron, 15(7), 1996, pp. 1079-1089
Starting from [MO(4)](-) (M = Tc, Re) the low-pressure (1 atm.) synthe
sis of the important starting material (NEt(4))(2)[MCl(3)(CO)(3)] coul
d be improved in terms of yield and time. These M(I) complexes were us
ed for the preparation of compounds containing the ''fac-M(CO)(3)'' mo
iety under ambient conditions. The substitution with the isocyanide li
gand CN-Bu(t) is described. In the case of rhenium, IR spectroscopical
investigations in the CO stretching region allowed the observation of
the stepwise formation of [Re(CNBu(t))(3)(CO)(3)](+). It could be dem
onstrated that Tc-99 NMR spectroscopy allows similar investigations, a
lthough not all types of intermediates could be detected. The structur
e of the complex [Tc(CN-Bu(t))(3)(CO)(3)](NO3) was elucidated by X-ray
diffraction analysis. Substitution with the protic ligand 2-mercaptoe
thanol HSCH2CH2OH revealed similar behaviour. Two intermediates were o
bserved with IR spectroscopical methods. The final product was the dim
er (NEt(4)) [Tc-2(mu-SCH2CH2OH)(3)(CO)(6)], the structure of which was
determined by X-ray diffraction.