36-Nuclear anionic cobalt(II) and nickel(II) complexes in solid-phase insertion reactions

The reactions of single crystals containing 36-nuclear anionic complexes of cobalt(II), (NBu4)8[Co36(H2O-κO)12(μ3-OH)20(μ4-Me2Mal-κ2O,O′)24(μ4-Me2Mal)6] · 2.5H2O ∙ CH3OH (I), and nickel(II), (NBu4)8[Ni36(H2O-κO)12(μ3-OH)20(μ4-Me2Mal-κ2O,O′)24(μ4-Me2Mal)6] · 6H2O ∙ 2C2H5OH (II) and (NHEt3)3[Ni36(NHEt3)(H2O-κO)12.25(μ3-OH)20(μ4-HMe2Mal-κ2O,O′)4(μ4-Me2Mal-κ2O,O′)20(μ4-Me2Mal)6] · 39H2O (III), with solutions of 1,4-dioxane and a 0.1 M solution of Dabco (Dabco is 1,4-diazabicyclo[2.2.2]octane) in EtOH are studied. An ethanol solution of Dabco dissolves the crystals of the complexes, whereas the insertion of the solvent molecules with single crystal retention (for the cobalt compound containing tetrabutylammonium cation, I), cracking (for the nickel analog, II), or dissolution (for the cobalt complex containing triethylammonium, III) occurs in 1,4-dioxane. The X-ray diffraction analyses show the substitution of the uncoordinated water and ethanol molecules in the starting compound by 1,4-dioxane molecules in the structure of compound I to form (NBu4)8[Co36(H2O-κO)12(μ3-OH)20(μ4-Me2Mal-κ2O,O′)24(μ4-Me2Mal)6] · 7C4H8O2 (IV), which is accompanied by a change in the conformation and the shift of tetrabutylammonium cations, indicating a possibility of the modification of the 36-nuclear d-metal complexes with the malonic acid derivatives in the solid-phase resolvation reactions (CIF files CCDC no. 1557499 (III) and 1557500 (IV)).