名称:
A complete series of tricarbonylhalidorhenium(I) complexes (abpy)Re(CO)3(Hal), Hal=F, Cl, Br, I; abpy=2,2′-azobispyridine: Structures, spectroelectrochemistry and EPR of reduced forms
摘要:
For the first time a complete set of tricarbonylhalidorhenium(I) complexes (Hal = F, Cl, Br, I) has been studied in a systematical fashion by example of (abpy)Re(CO)(3)(Hal), abpy = 2,2'-azobispyridine. Crystal structures of chloride, bromide and iodide analogues are now available, showing increasing planarization of the abpy ligand in that order. Cyclic voltammetry, EPR, IR and UV/Vis spectroelectrochemistry of the reduced forms [(abpy)Re(CO)(3)(Hal)](.-) illustrate that the four halide complexes differ only partially in their properties. The strongest deviations are observed for [(abpy)Re(CO)(3)F](.-) which is distinguished by the widest electrochemical potential range but most pronounced chemical lability. In the EPR spectrum the fluoride exhibits the highest isotropic g value (2.0085) and the lowest rhenium coupling constant, which is of the same magnitude (2 mT) as the detectable F-19 hyperfine splitting. (C) 2004 Elsevier B.V. All rights reserved.