Toward a square grid polymer: Electrochemistry of tentacled tetragonal star connectors, C{sub 4}R{sub 4}-Co-C{sub 5}(HgY){sub 5}, on mercury
Journal Article
·
· Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
- Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
- J. Heyrovsky Inst. of Physical Chemistry, Prague (Czech Republic)
Electrochemical reduction of cyclobutadienecyclopentadienylcobalt derivatives, C{sub 4}R{sub 4}-Co-C{sub 5}(HgY){sub 5} [R = C{sub 6}H{sub 5}-, Y = -SMe (3), -SCOMe (4), -SCH{sub 2}Ch{sub 2}SCH{sub 3} (5), -SCH{sub 2}CH{sub 2}SCOCH{sub 3} (6); R = p-EtOCOC{sub 6}H{sub 4}-, Y = -SEt (7), -SCOMe (8), -SCH{sub 2}CH{sub 2}SCH{sub 3} (9), -SCH{sub 2}CH{sub 2}SCOCH{sub 3} (10)], and the parent C{sub 4}R{sub 4}-Co-C{sub 5}H{sub 5} [R = C{sub 6}H{sub 5}- (11) and R = p -EtOCOC{sub 6}H{sub 4}- (12)] has been examined. Reversible one-electron metal-centered reduction of 11 ({minus}2.24 V vs Ag/AgCl) yields a stable radical anion. In 12, it takes place at {minus}1.70 V. In 3--10, similar metal-centered reduction occurs irreversibly, accompanied by an adsorption pre-wave at {minus}0.7 to {minus}1.15 V. The authors propose that the radical anion loses a {minus}HgSX substituent soon after it is formed. Electrochemical cleavage of the substituents occurs before the metal-centered reduction in 4 and 8 and afterward in the others. The cleaved thiolate fragments yield an anodic peak. In all compounds with ester groups, ester reduction is observed at {minus}2.1 to {minus}2.5 V.
- Sponsoring Organization:
- USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States); North Atlantic Treaty Organization, Brussels (Belgium); Government of the Czech Republic (Czech Republic)
- DOE Contract Number:
- FG03-94ER12141
- OSTI ID:
- 316065
- Journal Information:
- Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 49 Vol. 102; ISSN 1089-5647; ISSN JPCBFK
- Country of Publication:
- United States
- Language:
- English
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