Computational Experiments Probing the Adaptability of the [NCCH 2 ] − Electronic Structure to Various Bonding Environments
Résumé
Using combined geometry optimization and electronic analyses, it is examined how metal nature (alkali and Cu(I)), solvation (THF), ligands, and aggregation modulate the N‐ versus C‐bonding balance in metalated acetonitrile. C‐binding is energetically favored in covalent Cu(I) complexes, while lithiated species prefer N‐binding. Surprisingly, N‐metalated species do not all exhibit the expected ketenimine‐like character (CCN, lone pair on N), but a nitrile‐like one (C b C≡N, lone pair on C b ) also emerges from the natural bond orbital analyses. Ketenimines are stabilized by polarizing or covalent MN bonds, while nitriles are obtained with weakly coordinating cations or in anionic species. Notably, an external electric field can induce a similar electronic reorganization, thus revealing the electronic flexibility of metalated nitriles.
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