Chemical pathways for poly-anionic isomerisation in the metastable anions of tetra-deprotonated naphthalene: an intra-molecular inter-ring proton-transfer.
Phys Chem Chem Phys
; 19(18): 11571-11580, 2017 May 10.
Article
em En
| MEDLINE
| ID: mdl-28426056
A surprising chemical pathway involving an intra-molecular proton-transfer between the two different aromatic rings of naphthalene is revealed while exploring the isomerisation in the metastable tetra-anionic species of tetra-deprotonated naphthalene. The pathways are explored through quantum-mechanical computations employing a global reaction route mapping (GRRM) strategy. Notably, several other pathways traced exhibit interesting aspects of poly-anionic isomerisation in the multiply-charged metastable molecular anions, which can provide valuable insights into the mechanisms of ring closure and expansion leading to species like azulenes, cyclodecapentaene, and phenylvinylacetylene. The metastable poly-anionic species along the pathways were also analysed using a nuclear charge stabilisation procedure while employing conventional density functional theory (DFT) with the B3LYP exchange-correlation functional as well as long-range and dispersion corrected DFT/ωB97XD and DFT-D3 methods. Interestingly, the charge stabilisation method using the DFT/B3LYP was found to be more reliable than the dispersion corrected methods.
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MEDLINE
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En
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2017
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Article