Metal carbonyl chemistry. Part XX. A novel method for the synthesis of nonacarbonyl(fluoroalkylcarbon)tricobalt derivatives
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 14,p. 1449-1455
- https://doi.org/10.1039/dt9750001449
Abstract
The compounds [RCCo3(CO)9](R = F, CHF2, CF3, or C2F5) have been obtained in yields of 15–70% from reaction between the fluoroalkyltetracarbonylcobalt derivatives [(RCF2)Co(CO)4] and either sodium tetracarbonylcobaltate(–1), or octacarbonyldicobalt in the presence of donor solvents, such as tetrahydrofuran or ether. Reaction of Na[Co(CO)4] with [{(CO)4Co(CF2)}2] similarly gives [{(CO)9Co3C}2] in ca. 16% yield. Evidence is presented that the reaction of ClCO·(CF2)2·COCl or ClCO(CF2)3·COCl with an excess of Na[Co(CO)4] gives the compounds [(CO)9Co3C(CF2·CO2H)] and [(CO)9Co3C(CF2·CF2·CO2H)] respectively as major reaction products, in addition to the expected products [(CO)4Co(CF2)2Co(CO)4] and [(CO)4Co(CF2)3Co(CO)4]. Attempts to extend the reactions of [(CF3)Co(CO)4] or [(n-C3F7)Co(CO)4] to other carbonylmetal anions were unsuccessful, as was the attempted reaction of [(CF3Co(CO)3(PPh3)] with Na[Co(CO)4]. The preparation of [(CF3)2CF–Co(CO)4] is described, and its reaction with Na[Co(CO)4] has been shown to give a low yield of a product tentatively identified as [(CO)3Co(CO){C(CF3)2}Co(CO)3]. In the light of these findings possible mechanisms for the reaction are discussed.Keywords
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