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.

Periodical trends in [Co6E(CO)16]-clusters : Structural, synthetic and energy changes produced by substitution of P with As / R. Della Pergola, A. Sironi, V. Colombo, L. Garlaschelli, S. Racioppi, A. Sironi, P. Macchi. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 849–850:(2017 Nov 01), pp. 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

A. Sironi
;
V. Colombo;
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.
cobalt; arsenic; metal cluster; solid state structure; DFT calculations
Settore CHIM/03 - Chimica Generale e Inorganica
Settore CHIM/02 - Chimica Fisica
1-nov-2017
24-mag-2017
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/503876
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