A simple synthetic procedure (reaction between Re(CO)(5)Cl and 8-hydroxyqui
noline, HOX, in boiling toluene) leads to the dimeric complex Re-2(CO)(6)(O
X)(2). In coordinating solvents Re-2(CO)(6)(OX), undergoes dissociative sol
volysis (via a second order reaction) to form monomeric species of general
formula Re(CO)(3)(OX)solv. In non-coordinating media, however, the dimeric
complex remains unaffected. Molecular structures of both forms (which are i
n accord with IR absorption spectra) were confirmed by means of X-ray measu
rements. UV-VIS spectroscopic (absorption and emission) properties of both
newly synthesized Re(I) complexes, have been investigated and the differenc
es in their luminescence properties have been briefly discussed.