Abstract

The solvothermal reaction of (N(C 4H 9) 4) 2 [Re 2Cl 8] with trifluoroacetic acid and acetic anhydride leads to the new rhenium trifluoroacetate dimer N(C 4H 9) 4 [Re 2(OOCCF 3)Cl 6] (1) and to the rhenium carbonyl dimer Re 2(? 2-Cl) 2(CO) 8 as the rhenium-reduced byproduct. The reaction of the precursor complex 1 N(C 4H 9) 4 [Re 2(OOCCF 3)Cl 6] (1), with the organometallic carboxylic acid (CO) 6CO 2HCCCOOH leads to the cluster of clusters compound Re 2(OOCCCHCo 2 (CO) 6) 4-Cl 2 (2), which has the dimer structure of Re 2(OOCR) 4Cl 2. Cyclic voltammetric measurements show that Re 2(OOCCCHCo 2 (CO) 6) 4Cl 2 (2) has one reduction centered on the dirhenium core and a reduction centered on the cobalt atoms. DFT calculations have been used to rationalize the observed displacements of the voltammetric signals in Re 2(OOCCCHCo 2 (CO) 6) 4Cl 2 (2) compared to the parent ligand (CO) 6CO 2HCCCOOH and rhenium pivalate.