| Texto completo | |
| Autor(es): |
Simonova, Viktoriia M.
;
Pestova, Olga N.
;
Anufrikov, Yuri A.
;
Esposito, Breno P.
;
Khripun, Vasilii D.
Número total de Autores: 5
|
| Tipo de documento: | Artigo Científico |
| Fonte: | JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY; v. 149, n. 10, p. 11-pg., 2024-04-12. |
| Resumo | |
The thermal effect of a model oxo-transfer reaction with the participation of a tungsten-containing synthetic analog of the enzyme active site, [WO2(mnt)(2)](2-) (mnt = maleonitriledithiolate), has been determined for the first time. The value of the thermal effect indicates that the driving force of the oxo-transfer is the enthalpy factor. To determine the thermal effect of oxo-transfer, the dissolution enthalpies of the reaction participants in acetonitrile were determined: Delta H-sol(0 )(PPh3) = (24.9 +/- 0.8) kJ mol(-1), Delta H-sol(0 )(OPPh3)=(18.9 +/- 0.6) kJ mol(-1), and Delta H-sol(0 )([Bu4N](2)[WO2(mnt)(2)]) = (70.8 +/- 1.9) kJ mol(-1). In this study, the thermal effect of the transfer process of an oxygen atom from the tungsten complex [WO2(mnt)(2)](2-) to the PPh3 substrate was determined at different ratios of reagents: Delta H-r(0) = (- 109 +/- 4) kJ mol(-1). The catalytic cycle of PPh3 oxidation with oxygen in the presence of [WO2(mnt)(2)](2-) in acetonitrile solution was described calorimetrically. The absence of the reduced form of tungsten in the solution after the oxo-transfer reaction was shown spectroscopically, which confirms the role of the tungsten complex in the PPh3 oxidation as the catalyst. (AU) | |
| Processo FAPESP: | 21/10894-5 - Bioveiculadores de minerais para corais e zooxantelas |
| Beneficiário: | Breno Pannia Esposito |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |
| Processo FAPESP: | 22/05826-3 - Aplicações ambientais e farmacológicas da modulação dos níveis e propriedades físico-químicas de metais essenciais: uma proposta de cooperação Russo-Brasileira |
| Beneficiário: | Breno Pannia Esposito |
| Modalidade de apoio: | Auxílio à Pesquisa - Pesquisador Visitante - Internacional |