Dynamic in situ solvothermal reactions between ZnX2 (X = Cl, ClO4) and a heterocyclic disulfide

作者：Zhu, Hai-Bin^*; Deng, Wei; Xu, Liu-Long

来源：Transition Metal Chemistry, 2017, 42(7): 655-660.

DOI：10.1007/s11243-017-0171-7

• COORDINATION POLYMERS
• LIGAND SYNTHESIS
• CLEAVAGE
• CONSTRUCTION
• LUMINESCENCE
• SULFINATE
• COMPLEXES
• SULFONATE
• NETWORKS
• BONDS

Solvothermal reactions of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide) with ZnX2 (X = Cl, ClO4) in mixed CH3OH-CH2Cl2 solvent have been investigated. To better understand these reactions, solution analysis was conducted in parallel with single-crystal X-ray diffraction analysis of the in situ generated coordination complexes. At 120 A degrees C, solvothermal reaction of 2-ppds with ZnCl2 resulted in a discrete mononuclear coordination complex formulated as [ZnCl2(L1)] (1), in which the zwitterion L1 (1-methyl-4-(pyridin-2-yl)pyrimidin-1-ium-2-olate) was formed in situ from 2-ppds, and solution analyses based on TLC and ESI-MS further showed that the reaction solution also contains in situ transformed products of L2 (bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) and L3 (2-methoxy-4-(pyridin-2-yl)pyrimidine). At 90 A degrees C, solvothermal reaction between 2-ppds and Zn(ClO4)(2) led to a discrete mononuclear coordination complex formulated as [Zn(SH)(L2)]ClO4 (2) that features a terminally bound -SH group, while the reaction solution was also found to contain a library of in situ reaction products of 2-ppds including L1, L2, L3 and L4 ((4-(pyridin-2-yl)pyrimidin-2-yl) 4-(pyridin-2-yl)pyrimidine-2-sulfonothioate). Thus, the heterocyclic disulfide 2-ppds is transformed in situ into various organic products in a series of reactions involving C-S/S-S bond cleavage.

• 出版日期2017-10
• 单位东南大学