Details

Autor(en) / Beteiligte

• Huo, Bin
• Zhang, Xingyu
• Lu, Hai‐Gang
• Jin, Bo
• Yuan, Caixia
• Meng, Qingyong
• Wu, Yan‐Bo

Titel

Comments on “Planar Tetracoordinate Hydrogen: Pushing the Limit of Multicentre Bonding”

Ist Teil von

• Angewandte Chemie, 2024-05, Vol.136 (22), p.n/a

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Quelle

Wiley Blackwell Single Titles

Beschreibungen/Notizen

• In a recent communication (Angew. Chem. Int. Ed. 2024, 63, e202317312), Kalita et al. studied In4H+ system within the frame of single‐reference approximation (SRA) and found that the global energy minimum (1 a) adopted the singlet state and a planar tetracoordinate hydrogen (ptH), while the second lowest isomer (1 b) located 3.0 kcal/mol above 1 a and adopted the triplet state as well as non‐planar structure with a quasi‐ptH. They assessed the reliability of SRA by checking the T1‐diagnostic values of coupled cluster calculations. However, according to our multi‐configurational second‐order perturbation theory calculations at the CASPT2(12,13)/aug‐cc‐pVQZ (aug‐cc‐pVQZ‐PP for In) level, both 1 a and 1 b exhibit obvious multi‐referential characters, as reflected by their largest reference coefficients of 0.928 (86.1 %) and 0.938 (88.0 %), respectively. Moreover, 1 b is 5.05 kcal/mol lower than 1 a at this level, that is, what can be observed in In4H+ system is the quasi‐ptH. Multi‐configurational second‐order perturbation theory calculations revealed that the low‐lying isomers of In4H+ reported by Kalita et al. (Angew. Chem. Int. Ed. 2024, 63, e202317312) all showed the obvious multi‐reference characters and the desired D4h isomer with a planar tetracoordinate hydrogen (ptH) was only the fifth lowest isomer, which was 5.05 kcal/mol higher than the global minimum in C4v symmetry and having a quasi‐ptH, so the perfect ptH cannot be observed in In4H+ system.