Salvitti Chiara, Bandeira Nuno A G, Pepi Federico, de Petris Giulia, Troiani Anna
Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Rome, Italy.
Biosystems and Integrative Sciences Institute (BioISI)-, Departamento de Química e Bioquímica, Faculdade de Ciências Universidade de Lisboa, 8.5.53 - C8 Campo Grande, 1749-016, Lisboa, Portugal.
Chemistry. 2023 Aug 4;29(44):e202301221. doi: 10.1002/chem.202301221. Epub 2023 Jul 5.
Different oxidative pathways of sulfur dioxide promoted by ZnO(NO ) , Zn(NO ) and Zn(NO )(NO ) are revealed by a joint investigation by mass spectrometry and theoretical calculations. The reactions are triggered by [Zn -O ⋅] or by the low-valence Zn through oxygen ion transfer or electron transfer to SO , respectively. The NO ligands intervene in the oxidation only when sulfur dioxide is converted to SO or SO , leading to the formation of zinc sulfate and zinc sulfite coordinated to nitrate or nitrite anions. Kinetic analyses show that the reactions are fast and efficient, and theory discloses the elementary steps, namely oxygen ion transfer, oxygen atom transfer and electron transfer, occurring through similar energy landscapes for the three reactive anions.
通过质谱和理论计算的联合研究揭示了由ZnO(NO₃)₂、Zn(NO₃)₂和Zn(NO₃)(NO₂)促进的二氧化硫的不同氧化途径。这些反应分别由[Zn -O·]或低价Zn通过氧离子转移或电子转移至SO₂引发。仅当二氧化硫转化为SO₄²⁻或SO₃²⁻时，NO₃⁻配体才会介入氧化反应，导致形成与硝酸根或亚硝酸根阴离子配位的硫酸锌和亚硫酸锌。动力学分析表明这些反应快速且高效，理论揭示了三个反应性阴离子通过相似能量态势发生的基本步骤，即氧离子转移、氧原子转移和电子转移。
