Synthesis and reactivity of new heterodinuclear iron/rhenium Cx complexes of the formula (η5-C5Me5)Re(NO)(PPh3)(CC)n(η2-dppe)Fe(η5-C5Me5) (n=3, 4): Redox properties and a dicobalt hexacarbonyl adduct Academic Article uri icon

abstract

  • We report in this communication the synthesis and characterization of two Fe/Re heterodinuclear complexes 3n of formula (η5-C5Me5)Re(NO)(PPh3)(C{triple bond, long}C)n(η2-dppe)Fe(η5-C5Me5) (n = 3, 4) as well as the hexacarbonyl dicobalt adduct (4) of the hexatriynediyl complex 33. We show by cyclic voltammetry that the "electronic communication" between the organometallic endgroups and thereby the thermodynamic stability of the corresponding mixed-valent (MV) parent 3n+ is strongly influenced by bridge extension or by complexation of the [Co2(CO)6] fragment. In the case of the hexatriynediyl complex, the MV complex 33+ or 4 can be isolated by performing the chemical oxidation of 33 at low temperature. Spectroscopic studies of this compound and of other stable oxidized redox congeners should now help us to unravel how bridge extension modifies the electronic communication between the different redox-active endgroups in this family of unsymmetrically-substituted polyynediyl compounds. © 2008 Académie des sciences.

author list (cited authors)

  • Szafert, S., Paul, F., Meyer, W. E., Gladysz, J. A., & Lapinte, C.

citation count

  • 15

publication date

  • June 2008