A metallacarboxylic acid is a metal complex with the ligand CO2H. These compounds are intermediates in reactions that involve carbon monoxide and carbon dioxide, these species are intermediates in the water gas shift reaction.
Metallacarboxylic acids mainly arise by the attack of hydroxide on electrophilic metal carbonyl complexes. An illustrative synthesis is the reaction of a cationic iron carbonyl with a stoichiometric amount of base:
- [(C5H5)(CO)2FeCO]BF4 + NaOH → [(C5H5)(CO)2FeCO2H + NaBF4
When applied to simple metal carbonyls, this kind of conversion is sometimes called the Hieber base reaction. Decarboxylation of the resulting anion gives the anionic hydride complex. This conversion is illustrated by the synthesis of [HFe(CO)4]- from iron pentacarbonyl.
- Fe(CO)5 + NaOH → NaFe(CO)4CO2H
- NaFe(CO)4CO2H → NaHFe(CO)4 + CO2
Metallacarboxylic acids exist in equilibria with the carboxylate anions, LnMCO2-.
Many derivatives of metallacarboxylic acids have been prepared including metallacarboxylate esters (LnMCO2R), metallacarboxylic amides (LnMC(O)NR2). Derivatives of metalladithiacarboxylic acids are also known. They are prepared by treating anionic complexes with carbon disulfide.
- I.S.Kolomnikov, T.V.Lysyak, S.L.Rusakov, and Yu.Ya.Kharitonov "Metal-carboxylic Acids and Their Derivatives" Russ. Chem. Rev. 1988, vol. 57, pp. 406. http://iopscience.iop.org/0036-021X/57/5/R02.
- J. J. Brunet "Tetracarbonylhydridoferrates, MHFe(CO),: Versatile Tools in Organic Synthesis and Catalysis" Chem. Rev. 1990, volume 90. 1041-1059 1041. doi:10.1021/cr00104a006
- R. Duane Dombek, Robert J. Angelici, "Dicarbonyl(η5-Cyclopentadienylxthio-Carbonyl)Iron(1 +) Hexafluorophosphate(1 -) and Dicarbonyl(η 5-Cyclopentadienyl)-[(Methylthio)Thiocarbonyl]Iron" Inorganic Syntheses 1977, Volume 17, p. 100ff. doi:10.1002/9780470132487.ch29