Sutton Catherine C R, da Silva Gabriel, Franks George V
Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria, 3010 (Australia).
Chemistry. 2015 Apr 27;21(18):6801-5. doi: 10.1002/chem.201406516. Epub 2015 Mar 9.
A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal-carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate C-O bond lengths and O-C-O angle.
一个广泛使用的原理是，羧酸盐伸缩振动模式的波数在与金属中心键合时发生的变化可用于推断键合的几何结构是单齿还是双齿。我们已经用从头算模型对金属羧酸盐的水合配合物测试了这一原理，并表明它确实成立。通过对水溶液中一系列阳离子的乙酸根和甲酸根键合进行建模，来预测金属羧酸盐配合物的红外光谱，并报告了对称和反对称振动模式的波数。此外，我们已经表明，这些波数的变化主要是由于与金属的键合如何改变羧酸盐的C-O键长和O-C-O角。
