Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group

• Published in: Science China. Chemistry Vol. 40; no. 3; pp. 236 - 244
• Main Author: 姜月顺 柴向东 杨文胜 张东 曹云伟 诸真家 李铁津 Jean-Marie Lehn
• Format: Journal Article
• Language: English
• Published: Heidelberg Springer Nature B.V 01.06.1997
• Subjects: and; Bonding strength; derivatives; electrochemistry; electron; Energy levels; ferrocene; frontier; interactions; Molecular orbitals; orbital; Pushing; spectroscopy; substituents
• ISSN: 1674-7291; 1006-9291; 1869-1870; 1862-2771
• DOI: 10.1007/BF02877724

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