The interactions between two or more redox-active organometallic moieties, especially those of mixed valence metal centers with bridging organic ligands are a field of great interest.  These interactions, however, usually focus on through bond conjugation which allows for communication between the mixed valence metal centers. However, little is known about intramolecular, through-space effects in such systems.1                It has been shown2 that oxidation potential and adiabatic ionization energies of chalcogen atoms are greatly reduced due to through space X���p interactions (X=S, Se, Te).  To investigate the potential application of these through space interactions towards intramolecular electronic communication, a series of highly strained, bisferrocenyl thioethers were synthesized and characterized using X-ray crystallography, dynamic 1HNMR, cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry and photoelectron spectroscopy.  The mechanism of electronic communication between ferrocenyl redox centers was studied.                 The synthesized compounds were shown to be highly sterically constrained where conjugation was precluded, however significant electronic interactions were observed.

Through-space, intramolecular interactions of non-conjugated bisferrocenylthioethers

246th National Meeting (2013)

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