Abstract
New experiments involving electrochemistry, Auger spectroscopy and elemental analysis of films and film-forming compounds, as well as X-ray crystallography and electrochemistry of a key model compound, have been used to elucidate the linkage structure and probable mechanism of formation of oxidatively generated polymeric and copolymeric films of phenanthroline-containing complexes of ruthenium. Film formation evidently involves indirect electrochemical activation of coordinated 1,10-phenanthroline to nucleophilic attack by the non-coordinated pyridyl nitrogen of a dipyridyl ligand singly coordinated to a second metal center. The resulting linkage is comprised of a carbon/nitrogen bond with an excess positive charge residing on the nitrogen atom. Electrochemical oxidation of a complexed metal ion (typically Ru(II)) drives the polymerization by: (a) rendering the 4 site of phenanthroline significantly electrophilic, and (b) providing an oxidizing equivalent for eventual H atom elimination and pyridinium ion formation via an internal electron transfer sequence.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 23-29 |
| Number of pages | 7 |
| Journal | Journal of Electroanalytical Chemistry |
| Volume | 414 |
| Issue number | 1 |
| DOIs | |
| State | Published - Sep 26 1996 |
Funding
We thank Professor James Ibers for providing access to equipment for X-ray data collection. We thank the Office of Naval Research and the NSF Materials Research Center at Northwestern (DMR-9120521) for support of our work. JTH also gratefully acknowledges unrestricted support from the Dreyfus Foundation (Teacher-Scholar Award, 1991-1996).
Keywords
- Electropolymerization
- Film
- Mechanism
- Phenanthroline
- Ruthenium
ASJC Scopus subject areas
- Analytical Chemistry
- General Chemical Engineering
- Electrochemistry