Carbon monoxide oxidation by oxygen in water-acetonitrile solutions of palladium(II) bromide complexes in the presence of Co(II), Fe(II) and Mn(III) phthalocyaninates

I N Rusnak,S A Nikiforov,O N Temkin,S I Goloborod’Ko,S A Prokhorov,I V Oshanina,O L Kaliya,E A Robinova

doi:10.32362/2410-6593-2019-14-6-76-94

I N Rusnak, S A Nikiforov + Show 6 more

Open Access

https://doi.org/10.32362/2410-6593-2019-14-6-76-94

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Abstract

Objectives. The objective of this paper was to compare acetylene oxidative dicarbonylation that leads to maleic anhydride with a side reaction of CO oxidation by oxygen in a PdBr 2 -LiBr-H 2 C-CH 3 CN system and in the presence of insoluble (Co) and soluble (Co, Fe, and Mn) phthalocyaninates (PcM). Methods. To study the oxidation of CO to CO 2 , a kinetics method was used; UV and IR spectroscopy was used to determine the concentrations of initial and intermediate compounds. Results . The knetics of CO to CO 2 oxidation were investigated and the reactivity series of PcM in CO oxidation and maleic anhydride synthesis was characterized. A satisfactory correlation was observed between reaction rates and PcM concentration, as well as the nature of metal, in both processes. The IR measurements of concentrations of Pd(II) and Pd(I) intermediate carbonyl complexes, and CO 2 concentrations, have made it possible to hypothesize the mechanism of CO 2 generation. The effect of PcM concentration on the concentrations of Pd(II)(CO) in CO oxidation has been shown. Conclusions. Based on the data regarding CO oxidation and acetylene oxidative dicarbonylation, certain conditions have been proposed to effectively produce double-labeled maleic anhydride with 13 C (from 13 CO).

Highlights

The objective of this paper was to compare acetylene oxidative dicarbonylation that leads to maleic anhydride with a side reaction of CO oxidation by oxygen in a PdBr2–LiBr–Н2О–CH3CN system and in the presence of insoluble (Co) and soluble (Co, Fe, and Mn) phthalocyaninates (PcM)
Работа выполнена при финансовой поддержке Российского фонда фундаментальных исследований, номер проекта 16-29-10674 офи-м

Summary

Objectives

The objective of this paper was to compare acetylene oxidative dicarbonylation that leads to maleic anhydride with a side reaction of CO oxidation by oxygen in a PdBr2–LiBr–Н2О–CH3CN system and in the presence of insoluble (Co) and soluble (Co, Fe, and Mn) phthalocyaninates (PcM). Одной из практически важных реакций окислительного карбонилирования ацетилена (и алкинов) является реакция окислительного дикарбонилирования с образованием малеинового ангидрида (МА):. Реакция эффективно протекает в каталитической системе РdBr2 – LiBr – ацетонитрил (AN) – Н2О. Для оптимизации синтеза малеинового ангидрида в каталитической системе РdBr2 – LiBr – РсМ –AN – Н2О важно установить закономерности более простого процесса – побочной реакции окисления СО, включающей стадии, участвующие и в синтезе МА, а именно, образования интермедиата I и окисления гидридных комплексов палладия. В каталитической системе PdBr2–LiBr–РсМ–AN–H2O синтеза МА кинетика окисления СО не изучалась

Экспериментальная часть

Закономерности процесса окисления СО кислородом