Abstract
An almost linear (<Mn-Mn-Mn=132.25°) trinuclear manganese(II) complex [Mn3 (L)(N3 )4 ]⋅2 H2 O (1) of a decacoordinating N8 O2 donor ligand, H2 L, was synthesized and structurally characterized by means of single-crystal X-ray crystallography and mass spectrometry. All the MnII centers are in pseudo-octahedral geometry and wrapped by a single decacoordinating N8 O2 donor ligand. The central manganese atom (Mn2) is connected to two terminal manganese (Mn1 and Mn3) atoms by two bridging phenolate O atoms and two bridging azide N atoms. Compound 1 is the first example of a linear trinuclear model to show pronounced epoxidation of olefins by tert-butylhydroperoxide (TBHP) with a turnover number (TON) greater than 950. Though epoxidation of olefins by m-chloroperbenzoic acid (m-CPBA) was found to be complete within 20 minutes of mixing, the conversion was not more than 40 % and corresponding alcohols were found to be major products, whereas with H2 O2 as oxidant there was no visible catalytic epoxidation of olefins. Furthermore, the compound was characterized by temperature-dependent magnetic susceptibility measurements and a total spin ground state of St =15/2 was found.
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