| Autor: |
Foscato M; Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway., Occhipinti G; Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway., Hopen Eliasson SH; Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway., Jensen VR; Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of chemical information and modeling [J Chem Inf Model] 2024 Jan 22; Vol. 64 (2), pp. 412-424. Date of Electronic Publication: 2024 Jan 10. |
| DOI: |
10.1021/acs.jcim.3c01649 |
| Abstrakt: |
Methods for computational de novo design of inorganic molecules have paved the way for automated design of homogeneous catalysts. Such studies have so far relied on correlation-based prediction models as fitness functions (figures of merit), but the soundness of these approaches has yet to be tested by experimental verification of de novo-designed catalysts. Here, a previously developed criterion for the optimization of dative ligands L in ruthenium-based olefin metathesis catalysts RuCl 2 (L)(L')(═CHAr), where Ar is an aryl group and L' is a phosphine ligand dissociating to activate the catalyst, was used in de novo design experiments. These experiments predicted catalysts bearing an N-heterocyclic carbene (L = 9 ) substituted by two N-bound mesityls and two tert -butyl groups at the imidazolidin-2-ylidene backbone to be promising. Whereas the phosphine-stabilized precursor assumed by the prediction model could not be made, a pyridine-stabilized ruthenium alkylidene complex ( 17 ) bearing carbene 9 was less active than a known leading pyridine-stabilized Grubbs-type catalyst ( 18 , L = H 2 IMes). A density functional theory-based analysis showed that the unsubstituted metallacyclobutane (MCB) intermediate generated in the presence of ethylene is the likely resting state of both 17 and 18 . Whereas the design criterion via its correlation between the stability of the MCB and the rate-determining barrier indeed seeks to stabilize the MCB, it relies on RuCl 2 (L)(L')(═CH 2 ) adducts as resting states. The change in resting state explains the discrepancy between the prediction and the actual performance of catalyst 17 . To avoid such discrepancies and better address the multifaceted challenges of predicting catalytic performance, future de novo catalyst design studies should explore and test design criteria incorporating information from more than a single relative energy or intermediate. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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