Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen-Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes

Abstract

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.