Poly(ferrocenylpersulfide)s

The trithiaferrocenophanes $\rm (RC\sb5H\sb3)\sb2FeS\sb3$ (where R = t-Bu, H) were prepared by dilithiation of the t-Bu-substituted ferrocenes followed by treatment with elemental sulfur. t-BufcS$\sb3$ was obtained as the 1,3,1$\sp\prime$ isomer. In the case of (t-Bu)$\sb2$fcS$\sb3$, this species was obtained as the $1,3,1\sp\prime ,4\sp\prime$ isomer, as established by $\sp1$H NMR measurements and X-ray crystallography. The trisulfides were converted to the polymers $\rm\lbrack (RC\sb5H\sb3)\sb2FeS\sb2\rbrack\sb{n}$ upon desulfurization with Bu$\sb3$P, which was shown by $\sp{31}$P NMR spectroscopy to be converted to Bu$\sp3$PS. GPC measurements indicated that the (t-Bu)- and (t-Bu)$\sb2$- substituted polymers are polydisperse with \rm M\sb{n}=3,700 (M\sb{w}=26,000) and M\sb{n}=2,400 (M\sb{w}=19,000), respectively. The soluble ferrocenepersulfide polymers undergo reversible electrochemical oxidation in two steps, separated by 290 mV. The first oxidation potential is similar to that for the trisulfide monomer and is thought to correspond to oxidation of alternating Fe centers. The second oxidation converts the remaining Fe$\sp{\rm II}$ sites. Reduction of ((t-Bu)$\rm\sb2fcS\sb2\rbrack\sb{\rm n}$ with LiBHEt$\sb3$ gave (t-Bu)$\sb 2fc{\rm S\sb2Li\sb2}$, which can be reoxidized (I$\sb2$) to the polymer, sulfurized (S$\sb8$) to give the trisulfide, and selenized (Se$\sb8$) to give (t-Bu)$\sb2fc{\rm S\sb2Se}$.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Compton, David Lee

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Inorganic
• Chemistry, Polymer

Statement dc:rights

• Copyright 1996 Compton, David Lee

Language dc:language

eng

Identifier

9780591197785
AAI9712237
(UMI)AAI9712237

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22995