Comparative Study of Solvatomorphs of Stryker's Reagent Using MicroED and Quantum Mechanics

Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202502524. doi: 10.1002/anie.202502524. Epub 2025 May 22.

Abstract

The atomic position of hydrogen atoms in metal hydrides has been a long-standing structural question in inorganic chemistry given that hydride delivery is integral to diverse chemical reactions. Microcrystal electron diffraction (microED), with it's increased sensitivity toward hydrogen atoms relative to X-ray diffraction, offers a potential path to addressing this challenge. Herein, the first microED study of Stryker's reagent is reported, resulting in the structure of a new benzene solvate. Improved accuracy for hydrogen atom positions was obtained via a quantum crystallography (QCr) approach, Hirshfeld atom refinement (HAR). Structural and topological analysis supports edge bridging hydrides in the microED structure of a THF solvate form, consistent with previous diffraction studies. Interestingly, analysis of a new benzene solvate, discovered in this study, is consistent with mixed edge- and face-bridging hydrides.

Keywords: HAR; MicroED; QM‐MD; Quantum crystallography; Solvates; Solvatomorphs.