Synthesis and structure of [Mn 6O 2(O 2CPh) 10(EtOH) 4(H 2O)] ·. EtOH, a manganese aggregate containing three types of benzoate ligation. Isomerism in [Mn 6O 2(O 2CPh) 10] complexes

Abstract

The reaction of Mn(O 2CPh) 2·.4H 2O with KMnO 4 in warm ethanol in the presence of benzoic acid has been found to give, in addition to the previously reported “manganic benzoate”, the new hexanuclear mixed-valence manganese cluster [Mn 6O 2 (O 2CPh) 10(EtOH) 4(H 2O)]·.EtOH ( 1) in 40% yield. X-ray crystal structure determination at −172°C shows that the complex contains a distorted [Mn II 4Mn III 2O 2] 10+ core and, in addition to terminal EtOH and H 2O groups, three different types of benzoate ligation viz. μ 3-bridging, μ 2-bridging and monodentate terminal forms.