Verplancke, Hendrik ; Diefenbach, Martin ; Lienert, Jonas N. ; Ugandi, Mihkel ; Kitsaras, Marios‐Petros ; Roemelt, Michael ; Stopkowicz, Stella ; Holthausen, Max C. (2024)
Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen‐Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes.
In: Israel Journal of Chemistry, 2023, 63 (7-8)
doi: 10.26083/tuprints-00024689
Artikel, Zweitveröffentlichung, Verlagsversion
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Kurzbeschreibung (Abstract)
We showcase here a dramatic failure of CCSD(T) theory that originates from the pronounced multi‐reference character of a key intermediate formed in the benzaldehyde amidation by N‐atom transfer from Pd(II) and Pt(II) metallonitrenes studied recently in combined experimental and theoretical work. For detailed analysis we devised a minimal model system, for which we established reliable reference energies based on approximate full configuration interaction theory, to assess the performance of single‐reference coupled‐cluster theory up to the CCSDTQ(P) excitation level. While RHF‐based CCSD(T) theory suffered dramatic errors, in one case exceeding 220 kcal mol⁻¹, we show that the use of broken‐symmetry (BS) or Kohn‐Sham (KS) orbital references yields substantially improved CCSD(T) results. Further, the EOM‐SF‐CCSD(T)(a)* approach met the reference data with excellent accuracy. We applied the KS‐CCSD(T*)‐F12b variant as high‐level part of an ONIOM(KS‐CC:DFT) scheme to reinvestigate the reactivity of the full Pt(II) and Pd(II) metallonitrenes. The revised reaction pathway energetics provide a detailed mechanistic rationale for the experimental observations.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2024 |
| Autor(en): | Verplancke, Hendrik ; Diefenbach, Martin ; Lienert, Jonas N. ; Ugandi, Mihkel ; Kitsaras, Marios‐Petros ; Roemelt, Michael ; Stopkowicz, Stella ; Holthausen, Max C. |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen‐Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes |
| Sprache: | Englisch |
| Publikationsjahr: | 9 Februar 2024 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 2023 |
| Ort der Erstveröffentlichung: | Weinheim |
| Verlag: | Wiley-VCH |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Israel Journal of Chemistry |
| Jahrgang/Volume einer Zeitschrift: | 63 |
| (Heft-)Nummer: | 7-8 |
| Kollation: | 18 Seiten |
| DOI: | 10.26083/tuprints-00024689 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/24689 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichung DeepGreen |
| Kurzbeschreibung (Abstract): | We showcase here a dramatic failure of CCSD(T) theory that originates from the pronounced multi‐reference character of a key intermediate formed in the benzaldehyde amidation by N‐atom transfer from Pd(II) and Pt(II) metallonitrenes studied recently in combined experimental and theoretical work. For detailed analysis we devised a minimal model system, for which we established reliable reference energies based on approximate full configuration interaction theory, to assess the performance of single‐reference coupled‐cluster theory up to the CCSDTQ(P) excitation level. While RHF‐based CCSD(T) theory suffered dramatic errors, in one case exceeding 220 kcal mol⁻¹, we show that the use of broken‐symmetry (BS) or Kohn‐Sham (KS) orbital references yields substantially improved CCSD(T) results. Further, the EOM‐SF‐CCSD(T)(a)* approach met the reference data with excellent accuracy. We applied the KS‐CCSD(T*)‐F12b variant as high‐level part of an ONIOM(KS‐CC:DFT) scheme to reinvestigate the reactivity of the full Pt(II) and Pd(II) metallonitrenes. The revised reaction pathway energetics provide a detailed mechanistic rationale for the experimental observations. |
| Freie Schlagworte: | Computational Chemistry, Coupled-Cluster Theory, Electronic Structure, Nitrogen Atom Transfer, Singlet Biradicaloids |
| ID-Nummer: | Artikel-ID: e202300060 |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-246895 |
| Zusätzliche Informationen: | Special Issue:New Frontiers in Gas Phase Chemistry and Catalysis Dedicated to Prof. Helmut Schwarz on the occasion of his 80th birthday |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie) |
| Hinterlegungsdatum: | 09 Feb 2024 13:40 |
| Letzte Änderung: | 12 Feb 2024 07:14 |
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Verfügbare Versionen dieses Eintrags
- Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen‐Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes. (deposited 09 Feb 2024 13:40) [Gegenwärtig angezeigt]
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