The anionic cluster [Co6As(CO)16]- was synthesized through the reaction of Na[Co(CO)4] and arsenic acid in THF at room temperature. Crystallization from MeOH/2-propanol yielded two polymorphs that feature two slightly different isomers of the anion with the same PPh4+ cation. One of the isomers is very similar to the known [Co6P(CO)16]-, formed by four edge fused triangles, partially wrapping the main group atom. The other isomer features a deformed cage, which differs mainly for a non-bonding Co-Co distance. The reasons for this unprecedented stereochemistry, and the factors which may trigger this isomer, have been investigated by DFT calculations.
DELLA PERGOLA, R., Sironi, A., Colombo, V., Garlaschelli, L., Racioppi, S., Sironi, A., et al. (2017). Periodical trends in [Co6E(CO)16]- clusters: Structural, synthetic and energy changes produced by substitution of P with As. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 849-850, 130-136 [10.1016/j.jorganchem.2017.05.041].
Periodical trends in [Co6E(CO)16]- clusters: Structural, synthetic and energy changes produced by substitution of P with As
DELLA PERGOLA, ROBERTO
;SIRONI, ANNALISA;
2017
Abstract
The anionic cluster [Co6As(CO)16]- was synthesized through the reaction of Na[Co(CO)4] and arsenic acid in THF at room temperature. Crystallization from MeOH/2-propanol yielded two polymorphs that feature two slightly different isomers of the anion with the same PPh4+ cation. One of the isomers is very similar to the known [Co6P(CO)16]-, formed by four edge fused triangles, partially wrapping the main group atom. The other isomer features a deformed cage, which differs mainly for a non-bonding Co-Co distance. The reasons for this unprecedented stereochemistry, and the factors which may trigger this isomer, have been investigated by DFT calculations.
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