Fundamental Relation between Molecular Geometry and Real-Space Topology. Combined AIM, ELI-D, and ASF Analysis of Hapticities and Intramolecular Hydrogen–Hydrogen Bonds in Zincocene-Related Compounds

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-06, Vol.118 (24), p.4351-4362
• Main Authors: Mebs, Stefan, Chilleck, Maren Annika, Meindl, Kathrin, Hübschle, Christian Bertram
• Format: Article
• Language: English
• Subjects: Bonding; Chemical bonds; Hydrogen - chemistry; Hydrogen Bonding; Inspection; Metallocenes; Models, Molecular; Organometallic Compounds - chemistry; Physical chemistry; Quantum Theory; Skewed distributions; Sole; Thermodynamics; Topology
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp503667g

Despite numerous advanced and widely distributed bonding theories such as MO, VB, NBO, AIM, and ELF/ELI-D, complex modes of bonding such as M–Cp*(R) interactions (hapticities) in asymmetrical metallocenes or weak intramolecular interactions (e.g., hydrogen–hydrogen (H···H) bonds) still remain a challenge for these theories in terms of defining whether or not an atom–atom interaction line (a “chemical bond”) should be drawn. In this work the intramolecular Zn–CCp*(R) (R = Me, −(CH2)2NMe2, and −(CH2)3NMe2) and H···H connectivity of a systematic set of 12 zincocene-related compounds is analyzed in terms of AIM and ELI-D topology combined with the recently introduced aspherical stockholder fragment (ASF) surfaces. This computational analysis unravels a distinct dependency of the AIM and ELI-D topology against the molecular geometry for both types of interactions, which confirms and extends earlier findings on smaller sets of compounds. According to these results the complete real-space topology including strong, medium, and weak interactions of very large compounds such as proteins may be reliably predicted by sole inspection of accurately determined molecular geometries, which would on the one hand afford new applications (e.g., accurate estimation of numbers, types, and strengths of intra- and intermolecular interactions) and on the other hand have deep implications on the significance of the method.