Binding Features of {M(3d)(cbdc)₂} Blocks (M(3d)=V^IVO, Cu^II; cbdc^2–=Dianion of Cyclobutane‐1,1‐Dicarboxylic Acid) in Formation of Heterometallic Structures with d‐Metal Cations

Abstract

Compounds containing bis-chelate dianionic blocks {M(3d) (cbdc) 2 } 2-(M(3d) = V IV O, Cu II ) with cations VO 2 + and Cu 2 + chelated by two anions of dicarboxylic acid have been prepared as crystals when aqueous solutions of vanadyl sulfate VOSO 4 ⋅3H 2 O or copper sulfate CuSO 4 ⋅5H 2 O have been allowed to react with sulfates of d-metals (Mn II , Co II , Ni II , Zn II , and Cd II ) and barium salt of cyclobutane-1,1-dicarboxylic acid (H 2 cbdc = C 4 H 6 (CO 2 H) 2 ) in the 1:1:2 ratio. The nature of the M(3d) metal center has been found to influence on the structure of the heterometallic compounds formed. 1D polymers [M(VO) (cbdc) 2 (EtOH) 2 (H 2 O) 3 ] n (M = Mn (1), Co (2), Ni (3)), molecular dinuclear complex [Zn(VO)(cbdc) 2 (H 2 O) 5 ]⋅H 2 O (4), and 1D polymer {[Cd(VO)(cbdc) 2 (H 2 O) 5 ]⋅H 2 O} n (5) are formed when M(3d) = V IV O, whereas in the case of the bis-chelate block with the Cu II atom, ionic compounds [M(H 2 O) 6 ][Cu(cbdc) 2 (H 2 O)] (M = Mn (6), Co (7), Ni (8), Zn (9)) and 2D polymer {[CdCu(cbdc) 2 (H 2 O) 2 ] ⋅2H 2 O} n have been synthesized. The isolation of paramagnetic centers in compounds 1-10 is confirmed by magnetic measurements and EPR spectroscopy.

Barium(II)–Chromium(III) Coordination Polymers Based on Dimethylmalonate Anions: Synthesis, Crystal Structure, Magnetic Properties, and EPR Spectra

“…Thus, malonate anions can be coordinated to metal atoms to form stable bis‐ and tris‐chelate units, which can be connected to each other and to other metal centers via two carboxyl groups in different bridging coordination modes giving rise to new polynuclear molecules and coordination polymers. [ 5 ] Important features of malonic acid are the existence of its substituted analogs (H 2 R 1 R 2 mal) and the possibility of varying the substituent at the carbon atom that links two carboxyl groups, thereby making it possible to control the composition and structure of the resulting complexes. [ 6 ]…”

Coordination Polymers Based on Oxovanadium(IV) Butylmalonate Fragments and Potassium, Magnesium, and Cadmium Cations

“…4). This indicates that the radius of the d-metal cation exerts no effect on the structure of the heterometallic compound formed by the bis-chelate vanadyl fragments as it was observed for the compounds with cyclobutane-1,1-dicarboxylate anions (see [44]). Thus, like for copper(II) malonates, for the systems with oxidovanadium(IV), only the partial substitution of potassium cations by magnesium is shown to occur, regardless of the nature of the substituent in the malonate anion [28]…”

Impacts of Alkali Metals on the Structures and Properties of Fe(III) Heterometallic Cyclobutane-1,1-dicarboxylate Complexes

“…By varying the substituents in the methylene group of malonic acid, it is possible to change the structure and properties of the resulting compounds, which was previously demonstrated for homometallic complexes of manganese­(II), − cobalt­(II), − nickel­(II), , copper­(II), − etc. Moreover, the structure of malonate complexes of transition metals, and hence their properties, can be changed by introducing atoms of s-, d-, or f-elements into a compound. − To date, vast data on the synthesis, structural features, and properties of transition metal complexes (with the exception of iron) with anions of substituted malonic acids and atoms of s-elements have been collected.…”