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Another torture track for quantum chemistry: reinvestigation of the benzaldehyde amidation by nitrogen‐atom transfer from Platinum(II) and Palladium(II) metallonitrenes

Verplancke, Hendrik ; Diefenbach, Martin ; Lienert, Jonas N. ; Ugandi, Mihkel ; Kitsaras, Marios‐Petros ; Roemelt, Michael ; Stopkowicz, Stella ; Holthausen, Max C. (2023)
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, 63 (7-8)
doi: 10.1002/ijch.202300060
Article, Bibliographie

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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.

Item Type: Article
Erschienen: 2023
Creators: Verplancke, Hendrik ; Diefenbach, Martin ; Lienert, Jonas N. ; Ugandi, Mihkel ; Kitsaras, Marios‐Petros ; Roemelt, Michael ; Stopkowicz, Stella ; Holthausen, Max C.
Type of entry: Bibliographie
Title: Another torture track for quantum chemistry: reinvestigation of the benzaldehyde amidation by nitrogen‐atom transfer from Platinum(II) and Palladium(II) metallonitrenes
Language: English
Date: 2023
Place of Publication: Weinheim
Publisher: Wiley-VCH
Journal or Publication Title: Israel Journal of Chemistry
Volume of the journal: 63
Issue Number: 7-8
Collation: 18 Seiten
DOI: 10.1002/ijch.202300060
Corresponding Links:
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.

Uncontrolled Keywords: Computational Chemistry, Coupled-Cluster Theory, Electronic Structure, Nitrogen Atom Transfer, Singlet Biradicaloids
Identification Number: Artikel-ID: e202300060
Additional Information:

Special Issue:New Frontiers in Gas Phase Chemistry and Catalysis

Dedicated to Prof. Helmut Schwarz on the occasion of his 80th birthday

Classification DDC: 500 Science and mathematics > 540 Chemistry
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie)
Date Deposited: 12 Feb 2024 07:16
Last Modified: 12 Feb 2024 08:06
PPN: 515500917
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