Synthesis and Oxidation of Iron(II) Ferrocenylacetylide Diphosphine Complexes. A Novel Type of Mixed-Valence Complex
详细信息 查看全文
- 作者：Masaru Sato ; Yukiko Hayashi ; Shigekazu Kumakura ; Natsuko Shimizu ; Motomi Katada ; and Satoshi Kawata
- 刊名：Organometallics
- 出版年：1996
- 出版时间：January 23, 1996
- 年：1996
- 卷：15
- 期：2
- 页码：721 - 728
- 全文大小：308K
- 年卷期：v.15,no.2(January 23, 1996)
- ISSN：1520-6041
文摘
Some Fe(II) ferrocenylacetylide complexes, [(Cp orCp*)(PP)FeC
CFc], were prepared bythe photolysis of the corresponding carbonyl complexes [(Cp orCp*)(CO)2FeCCFc] in thepresence of diphosphines (PP = dppe, dppm, dmpe). The cyclicvoltammograms showedtwo quasi-reversible waves at -0.47 to -0.84 and +0.08 to +0.12V. The one-electron-oxidized species were isolated as relatively stable solids from thereaction of the neutralFe(II) complexes with DDQ or FcHPF6. The oxidizedcomplexes exhibited an intervalencetransfer band at 1295-1595 nm, and the interaction parameters werecalculated from theposition (
2 = (0.98-2.44) × 10-2).This suggests that these are highly electrondelocalizedmixed-valence complexes. The IR spectra (
CC =1956-1976 cm-1), the ESR spectra(appearance of one broad signal), and the Mössbauer spectra (QS= 2.00-2.26 mm s-1)support the above suggestion. The structure of[Cp(dppe)FeCCFC] was determined bysingle-crystal X-ray diffraction.
CFc], were prepared bythe photolysis of the corresponding carbonyl complexes [(Cp orCp*)(CO)2FeCCFc] in thepresence of diphosphines (PP = dppe, dppm, dmpe). The cyclicvoltammograms showedtwo quasi-reversible waves at -0.47 to -0.84 and +0.08 to +0.12V. The one-electron-oxidized species were isolated as relatively stable solids from thereaction of the neutralFe(II) complexes with DDQ or FcHPF6. The oxidizedcomplexes exhibited an intervalencetransfer band at 1295-1595 nm, and the interaction parameters werecalculated from theposition (2 = (0.98-2.44) × 10-2).This suggests that these are highly electrondelocalizedmixed-valence complexes. The IR spectra (CC =1956-1976 cm-1), the ESR spectra(appearance of one broad signal), and the Mössbauer spectra (QS= 2.00-2.26 mm s-1)support the above suggestion. The structure of[Cp(dppe)FeCCFC] was determined bysingle-crystal X-ray diffraction.