Peroxomolybdate(VI)-citrate and -malate complex interconversions by pH-dependence. Synthetic, structural and spectroscopic studies

Dalton Transactions : an International Journal of Inorganic Chemistry
Zhao-Hui ZhouHui-Lin Wan

Abstract

The reaction of potassium molybdate(VI) with biologically relevant ligands, citric and malic acids, in the presence of H2O2 was investigated for the effect of pH variations on the product pattern. That with citric acid led to the formation of the monomeric complex K4[MoO(O2)2(cit)].4H2O (1) in the pH range 7-9, and dimer K5[MoO(O2)(2-)(Hcit)H(Hcit)(O2)2OMo].6H2O (2) (H4cit = citric acid) at pH 3-6 through carboxylate-carboxylic acid hydrogen bonding. The relation with the previously identified K4[MoO3(cit)].2H2O (4) and K4[Mo2O5(Hcit)2].4H2O (5) were shown. These and other intermediates were shown to react in the pH range 3-6 to give a more stable species 2; the reaction sequence was demonstrated either by the protonation from 1 or the deprotonation of [MoO(O2)2(H2cit)](2-) (8). Evidence that 2 exists as a dimer in solution is presented. The reaction with (S)-malic acid afforded Delta-K(2n)[MoO(O2)2((S)-Hmal)]n.nH2O (3) (H3mal = malic acid) that was oxidized further to oxalato molybdate (11) by H2O2. The three complexes 1-3 were characterized by elemental analysis, UV, IR and NMR spectroscopies, in addition to the X-ray structural studies that show citrate and malate being coordinated as bidentate ligands via alpha-alkoxyl and ...Continue Reading

References

May 18, 2000·The Journal of Organic Chemistry· Di Valentin CN Rosch

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Citations

Dec 30, 2016·ACS Nano·Ali JawaidRichard A Vaia
Nov 7, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Yu-Chen YangHui-Lin Wan
Feb 18, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·M Luísa RamosHugh D Burrows
Dec 16, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Valeria Conte, Barbara Floris
Jul 22, 2021·Chemistry, an Asian Journal·Wenchao ChenXinyi Ye

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