1993 Fiscal Year Final Research Report Summary
Study on Novel Binuclear Heteronuclear Mixed-valence Complexes
| Project/Area Number |
04640488
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Saitama University |
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Principal Investigator |
SATO Masaru Chemical Analysis Center, 分析センター, 助教授 (90008863)
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| Project Period (FY) |
1992 – 1993
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| Keywords | ferrocenylacetylene / ruthenocenylacetylene / binuclear complex / mixed-valence complex / pentametylruthenocene |
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| Research Abstract |
From the viewpoint exploring the mechanism for induction of the functionality, e.g.electro-conductivity, in organometallic compounds, various transition-metal metallocenylacetylide complexes were examined.
1. Ru(II) ferrocenylacetylide complexes were synthesized and their one-electron oxidized complexes were successfully isolated. The structure of the complex was confirmed by X-ray analysis. It was shown by various spectral data that there was large electron-delocalization in these complexes.
2. Fe(II) ferrocenylacetylide complexes were synthesized by the metal-exchange reaction. In the one-electron exidized complexes the oxidized site was localized on the Fe atom of ferrocenyl moiety and the electron-delocalization between two Fe atoms was small.
3. Phosphine-coordinated Fe(II) ferrocenylacetylide complexes were synthesized by photo-irradiation in presence of bisphosphines. It was clear by various spectral data that there was large electron-delocalization in these one-electron oxidized complexes. The charge-transfer complex with DDQ, TCNQ, etc showed the electron-elocalization according with the electron-withdrowing ability of acceptor.
4. Pt(II) ferrocenylacetylide complexes were prepared in the reaction of ferrocenylacetylene with the chloroplatinum complexes. In the one-electron oxidized complexes there was a little electron-delocalization.
5. Ru(II) ruthenocenylacetylide complexes were prepared in the reaction of ruthenocenylacetylene with the chlororuthenium complexes. In the complexes stable two-electron oxidized complexes was isolated, because of the spin-pairing of the unpaied-electron on both the Ru atoms. Ru(II) pentamethyl-ruthenocenylacetylide complexes were also prepared.
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