Correction: Not antiaromaticity gain, but increased asynchronicity enhances the Diels–Alder reactivity of tropone

Abstract

Correction for ‘Not antiaromaticity gain, but increased asynchronicity enhances the Diels–Alder reactivity of tropone’ by Eveline H. Tiekink et al., Chem. Commun., 2023, 59, 3703–3706, https://doi.org/10.1039/D3CC00512G.

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In the original paper, the reactivity of tropone and its neutral and deprotonated hydrazone analogs was studied using the generalized gradient approximation functional BP86-D3(BJ) for geometries and the range-separated hybrid functional ωB97X-D for energies. The authors have since identified a technical issue in the implementation of the ωB97X-D functional in the ADF software package, specifically the dispersion correction. Therefore, they have recomputed all energetic values (the optimized geometries remain the same as in the original manuscript due to using BP86) with ZORA-ωB97X-D4/TZ2P and prepared new tables (Tables 1 and 2) and figures (Fig. 1 and 2) from these results.

The conclusions are congruent with the original ZORA-ωB97X-D/TZ2P results, while the absolute energy values have changed, and the relative energy of all stationary points are stabilized. The updated results are reported below.

All analyses are performed at the ZORA-ωB97X-D4/TZ2P¹ level of theory on the geometries optimized by ZORA-BP86-D3(BJ)/TZ2P. The results included in this correction act as an update to those previously given in the original publication. Please see the original publication for further details related to the methodology. The associated electronic supplementary information has also been updated with additional data for the calculations reported here.

Results

Table 1 Electronic energies (ΔE) of the stationary points (in kcal mol⁻¹) for the Diels–Alder reactions between M and 1, 2-prot, 2, 3-prot, and 3^ab

Diene	RC	TS1	INT	TS2	P
a Computed at ZORA-ωB97X-D4/TZ2P//ZORA-BP86-D3(BJ)/TZ2P. b See Fig. S1 and Table S1 for the transition state structures and Gibbs free energies (ESI).
1	−8.7	20.8			−38.5
2-prot	−9.0	21.1			−41.0
3-prot	−9.1	23.0			−37.0
2	−17.9	−7.8	−22.6	−18.8	−48.0
3	−8.6	7.2			−45.8

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Table 2 Energy decomposition analysis terms (in kcal mol⁻¹) of the Diels–Alder reactions between M and 1 and 2^a

Diene	ΔE	ΔEstrain	ΔEint	ΔVelstat	ΔEPauli	ΔEoi	ΔEdisp
a Computed at consistent TS-like geometries (CM⋯Cdiene = 2.160 Å) at ZORA-ωB97X-D4/TZ2P//ZORA-BP86-D3(BJ)/TZ2P.
1	19.9	33.8	−13.9	−49.8	94.1	−56.7	−1.6
2	−6.9	21.4	−28.3	−52.8	79.9	−53.9	−1.6

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Fig. 1 (a) Molecular orbital diagram with the most significant occupied orbital overlaps; (b) key occupied orbitals; and (c) the structures with key structural information (in Å) of the Diels–Alder reactions between M and diene 1 and 2, computed at consistent TS-like geometries (C_M⋯C_diene = 2.160 Å) at ZORA-ωB97X-D4/TZ2P//ZORA-BP86-D3(BJ)/TZ2P.

Fig. 2 Kohn–Sham molecular orbital diagrams with orbital energy levels and overlaps for (a) the normal electron demand π-HOMO_diene–π-LUMO_M; and (b) the inverse electron demand π-LUMO_diene–π-HOMO_M of the Diels–Alder reactions between M and diene 1 and 2, computed at consistent TS-like geometries (C_M⋯C_diene = 2.160 Å) at ZORA-ωB97X-D4/TZ2P//ZORA-BP86-D3(BJ)/TZ2P.

These updated energies, orbital overlaps, and orbital energy levels are provided to show that the major conclusions in the original publication remain, despite the aforementioned technical issues.

The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

References

1. (a) J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2008, 128, 084106; (b) E. Caldeweyher, S. Ehlert, A. Hansen, H. Neugebauer, S. Spicher, C. Bannwarth and S. Grimme, J. Chem. Phys., 2019, 150, 154122.

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