fac-IRe(CO)_3(dmso-O)_3](CF_3SO_3):a new versatile and efficient Re(I)precursor for the preparation of mono and poh nuclear compounds containing fac-[Re(CO)_3]~+ fragments

摘要

We show here that the new complex fac-[Re(CO)_3(dmso-O)_3](CF_3SO_3)(1),efficiently prepared in one step from [ReBr(CO)_5] and featuring a broad range of solubility,is,in general,a better precursor for the one-step synthesis of mono-and polynuclear inorganic compounds containing fac-[Re(CO)_3]~+ fragments compared to the commonly used(NEt_4)_2 fac-[ReBr_3(CO)_3] and fac-[Re(CO)_3(CH_3CN)_3](Y)(Y=PF_6,BF_4,ClO_4)species.Compound 1 is the first example of a Re(I)-dmso complex structurally characterized and confirms the rule that dmso is always O-bonded when trans to CO.The reactivity of 1 was tested in the one-step preparation of several new and known complexes.The O-bonded sulfoxides of 1 are replaced under mild conditions by tri-(L_3)and bidentate ligands(L_2)to produce fac-[Re(CO)_3(L_3)]~+ and fac-[Re(CO)_3(L_2)(dmso-O)]~+ compounds,respectively.An excess of monodentate ligands(L)and more forcing conditions are needed to prepare fac-[Re(CO)_3(L)_3]~+ compounds.The new compounds include fsc-[Re(CO)_3(bipy)(dmso-O)](CF_3SO_3)(4),that turned out to be an excellent precursor for binding the luminescent fac-[Re(CO)_3(bipy)]~+ fragment to polytopic ligands for the construction of more elaborate assemblies.One example reported here is the two-step preparation of fac-[{Re(CO)_3(bipy)}(mu-4,4'-bipy){Ru(TPP)(CO)}](CF_3SO_3)(8)(TPP=tetraphenylporphyrin).The X-ray structures of the new compounds 1,4,of the bis-porphyrin complex fac-[Re(CO)_3Cl(4'MPyP)_2](13)(4'MPyP=5-(4'pyridyl)-10,15,20-triphenylporphyrin),and of the rhenium-cyclophane [{(CO)_3Re(mu-OH)_2Re(CO)_3}_2(mu-4,4'-bipy)_2](15),among others,are described.Compound 1 might find useful applications in supramolecular chemistry(metal-mediated assembly of large architectures),in the in situ preparation of stable Re compounds to be used in nuclear medicine,and for the labeling of biomolecules.