Espinosa Ferao Arturo, García Alcaraz Antonio, Zaragoza Noguera Salvador, Streubel Rainer
Departamento de Quı́mica Orgánica, Facultad de Quı́mica, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain.
Institut für Anorganische Chemie, Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany.
Inorg Chem. 2020 Sep 8;59(17):12829-12841. doi: 10.1021/acs.inorgchem.0c01874. Epub 2020 Aug 12.
The stability and some characteristic bonding features of a variety of ligand (L)-stabilized phosphinidene complexes derived from adduct formation with halides, and both anionic or neutral O-donor bases were explored. Furthermore, the main features of L → P pnictogen bonding in such adducts were studied not only by using geometric criteria such as L-P bond distances and pyramidalization or planarity at P but also by turning the spotlight on bond-strength-related (including atoms-in-molecules-derived) parameters, thermodynamic stability dependence with electronic characteristics of the free ligand, and dative-bonding participation. We propose the new descriptor, τ, which, together with the sign and magnitude of ∇ρ at the bond critical point, constitutes the required criteria to differentiate L-P linkages as van der Waals interactions, dative bonding, or mostly covalent bonds.
研究了多种配体（L）稳定的次膦基配合物的稳定性以及一些特征键合特征，这些配合物是通过与卤化物以及阴离子或中性O供体碱形成加合物而得到的。此外，不仅通过使用诸如L-P键距离和P处的锥化或平面度等几何标准，而且通过关注与键强度相关的（包括源自分子中的原子的）参数、与游离配体的电子特性相关的热力学稳定性以及配位键参与情况，研究了此类加合物中L→P主族元素键合的主要特征。我们提出了新的描述符τ，它与键临界点处∇ρ的符号和大小一起，构成了区分L-P键为范德华相互作用、配位键或主要共价键所需的标准。
