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• W4223909442 abstract "• Catalytic transformation of CO and H 2 O to yield CO 2 and H 2 occurs in Water-gas shift reaction (WGSR) whereas the metallozyme-Carbon monoxide dehydrogenase (CODH), present in certain aerobic and anaerobic carboxidotrophic bacteria, catalyses the transformation of atmospheric CO to CO 2 with release of 2H + and 2e − . • In both cases the reactions proceed via an intermediate metallocarboxylic acid., the latter undergoes decarboxylation. Thus, synthetic approaches and related reaction pathways for stable M-COOH bonded complexes are imperative for further development of model systems to carry out CODH activity. In this manuscript we have summarized the different synthetic techniques with the corresponding reaction pathways for stabilizing metallocarboxylic acids and their structures. • Herein we demonstrate the importance of the chemistry of metallocarboxyllic acids in relation to CODH activity and WGSR. We have also taken into consideration the synthetic procedures of hydroxycarbonyls by selective nucleophilic attack of coordinated carbonyls by H 2 O/ OH‒, insertion of CO into M‒OH as well as insertion of CO 2 into M‒H bonds. The reaction pathways are also summarized. The role of hydrogen bonding in stabilizing MCOOH complexes in crystalline state as well as the nature of M‒C, C=O and C‒OH bonds have also been collated . Catalytic transformation of CO and steam to CO 2 and H 2 takes place in Water-gas shift reaction (WGSR) while the metallozyme-Carbon monoxide dehydrogenase (CODH) catalyses the conversion of atmospheric CO to CO 2 with release of 2H + and 2e − . Both reactions proceed via an intermediate metallocarboxylic acid. Thus, synthetic approaches and related reaction pathways for stabilizing M-COOH bonded complexes are imperative for further development of model systems to carry out CODH activity. This review summarizes the synthesis of structurally characterized hydroxy carbonyls via selective nucleophilic attack of water or alkali at the C-centre of metal carbonyls, insertion of CO 2 into M‒H bond and insertion of CO into M‒OH bond. The proposed pathways as well the nature of M‒C, C‒O and C‒OH bonds in the MCO 2 H moieties have also been described. Furthermore, stabilization of quite a few hydroxy carbonyls in crystalline state has also found to be attributed to intermolecular hydrogen bonding." @default.
• W4223909442 created "2022-04-19" @default.
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• W4223909442 date "2022-06-01" @default.
• W4223909442 modified "2023-09-26" @default.
• W4223909442 title "A perspective on exploration of synthetic reaction pathways of stable metallocarboxylic acids and structural features of MCOOH moiety" @default.
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• W4223909442 doi "https://doi.org/10.1016/j.jorganchem.2022.122355" @default.
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