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 are also called hydroxycarbonyls.[1]
Preparation
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:[2]
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.[3]
Fe(CO)5 + NaOH → NaFe(CO)4CO2H
NaFe(CO)4CO2H → NaHFe(CO)4 + CO2
Related compounds
Metallacarboxylic acids exist in equilibria with the carboxylate anions, LnMCO2−.
Metallacarboxylate esters (LnMCO2R) arise by the addition of alkoxide to metal carbonyl:
[LnM-CO]+ + ROH → [LnM-CO2R] + H+
Metallacarboxylic amides (LnMC(O)NR2) arise by the addition of amide to metal carbonyl:
[LnM-CO]+ + 2 RNH2 → [LnM-C(O)N(H)R] + RNH3+
Derivatives of metalladithiacarboxylic acids are also known. They are prepared by treating anionic complexes with carbon disulfide.[4]
References
^James R. Sweet, William A. G. Graham (1982). "Hydrido and Hydroxycarbonyl Compounds of the Carbonyl(η-cyclopentadienyl)nitrosylrhenium Group". Organometallics. 1 (7): 982–986. doi:10.1021/om00067a016.{{cite journal}}: CS1 maint: uses authors parameter (link)
^Kolomnikov, T. V.; Lysyak, Yu (1988). "Metal-carboxylic Acids and Their Derivatives". Russ. Chem. Rev. 57 (5): 406. Bibcode:1988RuCRv..57..406K. doi:10.1070/rc1988v057n05abeh003359. S2CID 250838386.
^Brunet, J. J. (1990). "Tetracarbonylhydridoferrates, MHFe(CO),: Versatile Tools in Organic Synthesis and Catalysis". Chem. Rev. 90 (6): 1041–1059. doi:10.1021/cr00104a006.
^Dombek, R. Duane; Angelici, Robert J. (1977). "Dicarbonyl(η5-Cyclopentadienylxthio-Carbonyl)Iron(1 +) Hexafluorophosphate(1 -) and Dicarbonyl(η 5-Cyclopentadienyl)-[(Methylthio)Thiocarbonyl]Iron". Inorganic Syntheses. 17: 100ff. doi:10.1002/9780470132487.ch29. ISBN9780470132487.
January 31, 2023
metallacarboxylic, acid, metallacarboxylic, acid, metal, complex, with, ligand, co2h, these, compounds, intermediates, reactions, that, involve, carbon, monoxide, carbon, dioxide, these, species, intermediates, water, shift, reaction, also, called, hydroxycarb. 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 are also called hydroxycarbonyls 1 Preparation EditMetallacarboxylic 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 2 C5H5 CO 2FeCO BF4 NaOH C5H5 CO 2FeCO2H NaBF4When 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 3 Fe CO 5 NaOH NaFe CO 4CO2H NaFe CO 4CO2H NaHFe CO 4 CO2Related compounds EditMetallacarboxylic acids exist in equilibria with the carboxylate anions LnMCO2 Metallacarboxylate esters LnMCO2R arise by the addition of alkoxide to metal carbonyl LnM CO ROH LnM CO2R H Metallacarboxylic amides LnMC O NR2 arise by the addition of amide to metal carbonyl LnM CO 2 RNH2 LnM C O N H R RNH3 Derivatives of metalladithiacarboxylic acids are also known They are prepared by treating anionic complexes with carbon disulfide 4 References Edit James R Sweet William A G Graham 1982 Hydrido and Hydroxycarbonyl Compounds of the Carbonyl h cyclopentadienyl nitrosylrhenium Group Organometallics 1 7 982 986 doi 10 1021 om00067a016 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint uses authors parameter link Kolomnikov T V Lysyak Yu 1988 Metal carboxylic Acids and Their Derivatives Russ Chem Rev 57 5 406 Bibcode 1988RuCRv 57 406K doi 10 1070 rc1988v057n05abeh003359 S2CID 250838386 Brunet J J 1990 Tetracarbonylhydridoferrates MHFe CO Versatile Tools in Organic Synthesis and Catalysis Chem Rev 90 6 1041 1059 doi 10 1021 cr00104a006 Dombek R Duane Angelici Robert J 1977 Dicarbonyl h5 Cyclopentadienylxthio Carbonyl Iron 1 Hexafluorophosphate 1 and Dicarbonyl h 5 Cyclopentadienyl Methylthio Thiocarbonyl Iron Inorganic Syntheses 17 100ff doi 10 1002 9780470132487 ch29 ISBN 9780470132487 Retrieved from https en wikipedia org w index php title Metallacarboxylic acid amp oldid 1130279898, wikipedia, wiki, book, books, library,
