Metal-coordination Induced In-situ Reactions Of Organic N-containing Heterocyclic Disulfide Ligand

N-containing heterocycle disulfide ligands are prone to undergo a variety of in situ reactions induced by different metal ions, such as the oxidative cleavage of S-S bond, reductive cleavage of S-S bond, S-C bond scission, even multiple bonds breaking concurrent with rearrangement reactions, which provide ample opportunities to build new metal-organic sulfur-containing heterocyclic framework especially those inaccessible via direct methods.As continuation of our previous work, we further investigate in situ reactions of 2-ppds (2-ppds= di[4-(pyridin-2-yl)pyrimidinyl]disulfide) under different conditions (ambient solution reaction and solvothermal reaction). By combination of different metal salt and solvent, twelve unprecedented in situ-generated coordination compounds have been discovered, [N(L1)(NO3)2] (1)(L1:bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) {[Ag2(L2)2] 2CH3CN}n (2)(L2:4-(pyridin-2-yl)pyrimidine-2-sulfonic)? [Cu(L3)2H20)](C104)2 (3)(L3:4-(pyridin-2-yl)pyrimidin-2-ol)? [Co(L4)2]ClO4·2CH3OH·H2O(4)(L4:4-(2-pyridyl) pyrimidin-2-disulfide anion)? [Cu(2-ppds)(H20)](C104)2(5)? [Cu(2-ppds)Br]2(CuBr4) (6)? [Cu(L3)2](ClO4)2(7)? [Cu4(L5)4] (8)((L5:4-(pyridin-2-yl)pyrimidine-2-thiol))? [Cu(L1)Cl(NH3)]C1 (9)? [Zn(L6)Cl2] (10)(L6:1-methyl-4-(pyridin-2-yl)pyrimidin-2-ol)? [Zn(L6)(SH)2](11)?[Zn(L1)(SH)](ClO4)(12).Single-crystal X-ray diffraction analyses of all resulted coordination compounds reveal that not only the selected metal ion but also the solvent system, temperature even the counter-anion have a profound effect on the in situ reactions in terms of reaction type and in situ-resulted organic products.