Complementary bonding analysis of the N–Si interaction in pentacoordinated silicon compounds using quantum crystallography

Malte Fugel (1) , Maksym Ponomarenko (2) , Maxie Hesse (1) , Lorraine Malaspina (1) , Florian Kleemiss (1) , Kunihisa Sugimoto (3, 4) , Alessandro Genoni (5) , Gerd-Volker Röschenthaler (2) , Simon Grabowsky (1)

1 Institut für Anorganische Chemie und Kristallographie = Institute of Inorganic Chemistry and Crystallography [Universität Bremen]
2 Jacobs University = Constructor University [Bremen]
3 JASRI - Japan Synchrotron Radiation Research Institute [Hyogo]
4 iCeMS - Institute for Integrated Cell-Material Sciences
5 LPCT - Laboratoire de Physique et Chimie Théoriques

Electronic supplementary information (ESI) available: characterization of compounds, crystallographic details, coordinates of optimized structures. CCDC: 1937643, 1937692, 1937940. Abstract The N-Si interaction in two pentacoordinated silicon compounds is investigated based on a complementary bonding analysis, which consists of bonding descriptors from real space and orbital space. These are derived from X-ray wavefunction refinements of high-resolution X-ray diffraction data of single crystals and from isolated-molecule theoretical wavefunctions. DELETED The two pentacoor-dinated compounds only differ in one methylene group, so that the amino substituent is more flexible in one of the structures, hence probing the attractive or repulsive character of the N-Si interaction. All studies suggest weak dative interactions, which do, however, greatly influence the character of the Si-F bond: A strong N-Si interaction results in a weakened Si-F bond, which is quantified in this study experimentally and theoretically.

Domains: Theoretical and/or physical chemistry; Cristallography

Malte Fugel, Maksym Ponomarenko, Maxie Hesse, Lorraine Malaspina, Florian Kleemiss, et al.. Complementary bonding analysis of the N–Si interaction in pentacoordinated silicon compounds using quantum crystallography. Dalton Transactions, 2019, 48 (43), pp.16330-16339. ⟨10.1039/C9DT02772F⟩. ⟨hal-02324017⟩