Automated Building of Organometallic Complexes from 3D Fragments

Abstract

A method for the automated construction of three-dimensional (3D) molecular models of organometallic species in design studies is described. Molecular structure fragments derived from crystallographic structures and accurate molecular-level calculations are used as 3D building blocks in the construction of multiple molecular models of analogous compounds. The method allows for precise control of stereochemistry and geometrical features that may otherwise be very challenging, or even impossible, to achieve with commonly available generators of 3D chemical structures. The new method was tested in the construction of three sets of active or metastable organometallic species of catalytic reactions in the homogeneous phase. The performance of the method was compared with those of commonly available methods for automated generation of 3D models, demonstrating higher accuracy of the prepared 3D models in general, and, in particular, a much wider range with respect to the kind of chemical structures that can be built automatically, with capabilities far beyond standard organic and main-group chemistry.

Redox Control of Aluminum Ring-Opening Polymerization: A Combined Experimental and DFT Investigation

“…[86][87][88][89][90][91][92][93][94] and predictive studies. [95][96][97][98][99][100][101][102][103][104] To gain a better understanding of the polymerization processes discussed above, detailed theoretical studies were essential. Our group previously reported DFT calculations on redox switchable polymerization by cerium.…”

Stabilization of activated fragments by shell‐wise construction of an embedding environment

“…Particularly the introduction of multidentate ligands leads to a stabilization of the scaffold around the transition metal center due to the chelate effect . In recent work, Jensen and coworkers emphasized the necessity of including chelate ligands in their molecular design approaches.…”

“…Particularly the introduction of multidentate ligands leads to a stabilization of the scaffold around the transition metal center due to the chelate effect. [28] In recent work, Jensen and coworkers [29][30][31][32] emphasized the necessity of including chelate ligands in their molecular design approaches. As the chelate effect on the overall stability of a complex is an entropy effect driven by the release of monodentate ligands from the binding sites then occupied by the multidentate ligand, it is not covered by our design process that relies on electronic energy considerations of only a single species.…”

molSimplify: A toolkit for automating discovery in inorganic chemistry

“…Instead, users have relied on searching commercial databases of experimentally characterized compounds. More recently, fragment‐based and rules‐based structure generation tools have been developed for 3D coordinate generation, as long as free‐to‐use fragments are placed into a predefined database, but the seamless connection to first‐principles modeling in an open source framework is not yet available.…”