Inorganica Chimica Acta
Inorganica Chimica Acta
4 years ago

The not-so-simple coordination chemistry of alkali-metal cations Li+, Na+ and K+ with one carbonate anion: A study using density functional and atoms in molecules theories

The not-so-simple coordination chemistry of alkali-metal cations Li+, Na+ and K+ with one carbonate anion: A study using density functional and atoms in molecules theories
A total of 23 new complexes in the series (CO3)M y y −2 (M=Li, Na or K; y =1–5) have been optimized using DFT, adding to known planar complexes (CO3)M y y−2 (M=Li or Na; y =1 or 2) and (CO3)M y y−2 (M=Na; y =3). Planar structures are the most stable for: M=Li, y =1–4; M=Na, y =1–3; M=K, y =1–3. For M=Na, three non-planar structures occur over a range in electronic energy of ca. 9kJ/mol when y =4, while for M=K only a single, non-planar structure occurs for y =4. For M=Li, Na or K, two non-planar structures were the only ones found for y =5. The CO3 moiety was found to be planar in all new species except for new isomers of (CO3)M− (M=Na or K) that have perpendicular (π-like) CO3:M bonding. No evidence was found for any stable species when y =6. Atomic charges were calculated by the AIM method for most of the new species and confirm that the CO3: M bonding is highly ionic. Stepwise complexation energies have been calculated for the addition of M+ to the most stable form of (CO3)M y −1 y −3 to give the most stable form of (CO3)M y y −2, for y =1–5. The stepwise formation reactions are exothermic for all the metals when y =1–3, but endothermic for all the metals when y =4 or 5. However, addition of four or five M+ to one CO3 2− is exothermic overall for all three metals.

Publisher URL: www.sciencedirect.com/science

DOI: S0020169317307144

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