Temperature effect on the conversions of phthalato and maleato manganese(II) complexes with diamine ligands |
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| Authors: | Jin-Mei Yang Hui Zhang Shi-Jie Lu |
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| Institution: | a State Key Laboratory for Physical Chemistry of Solid State Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China |
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| Abstract: | 1,10-Phenanthroline hydrogen phthalato manganese(II) dimer Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1), monomeric phenanthroline phthalato manganese(II) monomer Mn(phth)(phen)2(H2O)] · 2.5H2O (2), 2,2′-bipyridine phthalato manganese(II) polymer Mn(phth)(bpy)(H2O)2]n (3) and 1,10-phenanthroline maleato polymer Mn(male)(phen)(H2O)2]n · 2nH2O (4) (H2phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn-syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer Mn(male)(phen)]n · nH2O (5) with dehydration in warm solution. |
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| Keywords: | Phthalate Maleate Manganese(II) Coordination polymer Conversion |
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