A structural systematic study of semi-rigid ferrocene derivatives as a 3 x 3 metallocene isomer grid: p-/m-/o-(FcC(6)H(4))CONH(p-/m-/o-C6H4) CO2Et, [Fc = (eta(5)-C5H5) Fe(eta(5)-C5H4)]

作者：Gallagher John F^*; Alley Steven; Lough Alan J

来源：Inorganica Chimica Acta, 2016, 444: 113-125.

DOI：10.1016/j.ica.2016.01.028

• Amide
• Assembly
• Ferrocene
• Interactions
• Isomer grid
• Structural systematics

The nine ethyl 4-/3-/2-{[(4-/3-/2-ferrocenylphenyl)carbonyl]amino}benzoates, {4-/3-/2-FcC(6)H(4)-CONH-(4-/3-/2-C6H4)CO2Et, where Fc = (eta(5)-C5H5)Fe(eta(5)-C5H4)} have been synthesised by coupling either the para- ,meta- or ortho(ferrocenyl) benzoic acids (FcC(6)H(4)COOH), or their acid chlorides (FcC(6)H(4)COCl) with ethyl p-/m-/o-aminobenzoates, H2NC6H4CO2Et using (i) 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxy-benzotriazole (HOBt) or (ii) acid chloride coupling reactions. The isomers were characterised by spectroscopic techniques; single crystal X-ray diffraction structures of all nine isomers are reported and reveal the inherent linearity of the para- para substituted isomer (pp) compared to the twisted geometry of the ortho-ortho system (oo). Intra-/intermolecular interactions and distinct patterns of molecular aggregation are evaluated and correlated with physicochemical measurements showing distinct trends. A rich and somewhat congested amide center dot center dot center dot amide hydrogen bonding is noted in (mp) and (mm), contrasting with a lack of amide center dot center dot center dot amide interactions in (pp) and (pm) and unexpected amide center dot center dot center dot ester hydrogen bonding in dimers of (om). The series highlights the unpredictable nature of molecular assembly.

• 出版日期2016-4-1