Preparation and crystal structures of MnII, mixed-valent MnII/MnIII, and MnIII polymeric compounds
| Autor: | Tasiopoulos, Anastasios J., Harden, N. C., Abboud, K. A., Christou, George |
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| Přispěvatelé: | Tasiopoulos, Anastasios J. [0000-0002-4804-3822] |
| Rok vydání: | 2003 |
| Předmět: |
crystal structure
crystallization oxidation Supporting electrolyte Stereochemistry polymer Crystal structure law.invention Solid state Inorganic Chemistry Mn compounds law electrolysis Materials Chemistry Molecule Physical and Theoretical Chemistry Crystallization crystallography Polymeric Dissolution Valence (chemistry) Chemistry article Comproportionation Magnetic susceptibility structure analysis Crystallography polymerization molecular interaction Crystal structures manganese cluster analysis |
| Zdroj: | Polyhedron |
| ISSN: | 0277-5387 |
| DOI: | 10.1016/s0277-5387(02)01262-7 |
| Popis: | The preparation and crystal structures of three polymeric Mn compounds are reported. The comproportionation reaction between Mn(OAc)2·4H2O and KMnO4 in MeOH-AcOH (2:3) leads to isolation of {[Mn(OH)(OAc)2]·AcOH·H2O}n (1). The structure consists of chains of [Mn(μ-OH)(μ-OAc)2Mn] triply-bridged units. The chains are linked into 3D networks by hydrogen-bonding interactions involving the AcOH and H2O molecules of crystallization. Oxidation of [Mn12O12(O2CPh)16 (H2O)4] by controlled potential electrolysis in CH2Cl2 with NBu2nPF6 as supporting electrolyte yields a brown solution which slowly turns purple and then pale yellow. Deep purple crystals, obtained by addition of hexanes, were identified crystallographically as {(NBu4n])[Mn2(O2 PF2)6]·2/3CH2 Cl2}n (2), which is mixed-valent and consists of a chain of [MnII(μ-O2PF2)3 MnIII] triply-bridged units. Bond distances, bond valence sum calculations, and a Jahn-Teller (JT) axial elongation at the MnIII sites confirm a trapped-valence situation. Dissolution of Mn(OAc)2·4H2O in EtOH results in a subsequent crystallization of a white solid analyzing as [Mn(OAc)2·3/8H2O] (3a). Crystals grown from MeOH-Et2O were structurally identified as [Mn4(OAc)8(MeOH)2]n (3b), and consist of Y-shaped Mn4 units bridged by AcO- groups to give a 3D network. Variable-temperature, solid-state magnetic susceptibility studies establish that 1, 3a and 3b are antiferromagnetically coupled to give diamagnetic ground states. © 2002 Elsevier Science Ltd. All rights reserved. 22 1 133 143 Cited By :30 |
| Databáze: | OpenAIRE |
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