| Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group |
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| 作者姓名： | 姜月顺 柴向东 杨文胜 张东 曹云伟 诸真家 李铁津 Jean-Marie Lehn |
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| 作者单位： | Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Department of Chemistry Jilin University Changchun 130023 China，Chimie des Interactions Moléculaires Collège de France 11 Place Marcelin Berthelot 75005 Pairs France |
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| 基金项目： | Project supported by the National Natural Science Foundation of China |
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| 摘 要： | The frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group were analyzed based on the electrochemical,UV visible spectral and spectroelectrochemical results of five ferrocene derivatives,R-Fc-A1(PⅠ),A1-Fc-A1(PⅡ),D-Fc-R (PⅢ),D-Kc-A1(PIV) and D-Fc-A2(PV)(R,CH2OH;A1 CHO;A2,CH=C(CN)2 and D,(C18H37)2N-C6H4-CH=CH) It was found that there are strong interactions of the LUMO (πA) of electron drawing substituents with le2g(dxy,dx2 y2)and e2u of the ferroeenyl group because the energy levels of πA and e2g,C2U of (Cp )2 are close,which lower not only the energy levels of bonded orbits,πA+ and dx2-y2+πA] of PⅠ,PⅡ,PⅣ and PⅤobviously,but also those of their non-bonded orbu dxy For PⅢ,PⅣ and PⅤ,there are strong interactions of HOMO(πD) of the electron pushing substituent with le of the ferrocenyl group because the levels of πD and e of (Cp)2 are close,which result in the formation of anti-bonded orbit,πD- and bonded orbit
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| 收稿时间： | 20 August 1996 |
Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group |
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| Yueshun Jiang,Xiangdong Chai,Wensheng Yang,Dong Zhang,Yunwei Cao,Zhenjia Zhu,Tiejin Li,Jean-Marie Lehn.Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group[J].Science in China(Chemistry),1997,40(3):236-244. |
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| Authors: | Yueshun Jiang Xiangdong Chai Wensheng Yang Dong Zhang Yunwei Cao Zhenjia Zhu Tiejin Li Jean-Marie Lehn |
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| Institution: | (1) Jilin University, Department of Chemistry, 130023 Changchun, China;(2) Chimie des Interactions MolPculaires, College de France, 11 Place Marcelin Berthelot, 75005 Pairs, France |
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| Abstract: | The frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group were analyzed based on
the electrochemical, UV-visible spectral and spectroelectrochernical results of five ferrocene derivatives, R-Fc-A1(P1), A1-Fc-A1(PII), D-Fc-R (PIII), D-Fc-A1(PIV) and D-Fc-A2(PV) (R, CH2OH; A1 CHO; A2, CH = C(CN)2 and D, ((318H37)2N-C6&-CH = CH). It was found that there are strong interactions of the LUMO (π
a*
) of electron drawing substituents with 1e2g (dry, dr2 - y2) and e2u(ϕ4u, ϕ5u) of the ferrocenyl group because the energy levels of πA
* and e2g, e2u of (Cp-)2 are close, which lower not only the energy levels of bonded orbits πA
*+ϕ4u] and dx
2\t-y2 of PI, PII, PIV and PV obviously, but also those of their non-bonded orbit,dxy For PIII, PIV and PV, there are strong interactions of HOMO (πD) of the electron pushing substituent with lelu (ϕ2u, ϕ3u) of the ferrocenyl group because the levels of πD and eluof (Cp-)2 are close, which result in the formation of anti-bonded orbit, πD\t-ϕ3u], and bonded orbit, ϕ3u
+πD].
Project supported by the National Natural Science Foundation of China |
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| Keywords: | ferrocene derivatives frontier orbital interactions electron pushing and drawing substituents electrochemistry spectroscopy |
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