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Synthesis and Structural Characterization of Trimanganese‐Containing Polyoxovanadates with Carboxylate Ligands
Author(s) -
Maruyama Tatsuya,
Kikukawa Yuji,
Kawamoto Keisuke,
Hayashi Yoshihito
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601274
Subject(s) - chemistry , acetonitrile , carboxylate , dimer , ligand (biochemistry) , crystal structure , alkyl , benzoic acid , stereochemistry , crystallography , tetraethylammonium , medicinal chemistry , organic chemistry , potassium , receptor , biochemistry
A trimanganese core containing polyoxovanadate {Et 4 N} 5 [Mn 3 (OAc)(H 2 O)V 10 O 30 ] ( I ; OAc = acetate) was synthesized by the reaction of {Et 4 N}[VO 3 ] with Mn(OAc) 2 (0.3 equiv.) in acetonitrile. The trimanganese core possesses a bridging acetate ligand. To demonstrate the ligand‐exchange properties of I , its reaction with benzoic acid (1 equiv.) was conducted and {Et 4 N} 5 [Mn 3 (OBz)(H 2 O)V 10 O 30 ] ( II ; OBz = benzoate) was formed quantitatively. By using a dicarboxylate, the inorganic–organic–inorganic hybrid {Et 4 N} 10 [{Mn 3 (H 2 O)V 10 O 30 } 2 {OOC(CH 2 ) n COO}] [ n = 3 ( III ) and n = 4 ( IV )] compounds were synthesized. To compensate the negative–negative repulsion between the anionic groups with a 5– charge, tetraethylammonium cations are sandwiched between the anionic groups in the crystallographic packing. Despite the differences in the bridging carbon numbers, both complexes have the same orientation in the crystal state except for the conformation of the alkyl chains, which suggests the presence of a unique interaction with an anion–cation–anion motif to form V‐shaped dimer configurations.