Steric Control in Low-Valent Mn Diamide Complexes: Contrasting Magnesium and Manganese in N2 and Benzene Activation

Reduction of MnII precursors with bulky diamide ligands provided access to a complex with the longest known Mn–Mn bond and to a rare example of N2 activation at high-spin MnI centers. While some instructive parallels can thus be drawn to observations made for Mg analogues, the accessibility of filled d orbitals in the respective MnI intermediates leads to a distinct behavior toward benzene that undergoes an oxidative addition.通过大位阻二酰胺配体还原二价锰（Mn(II)）前驱体，我们成功获得了具有已知最长锰-锰键的配合物，同时得到了一例在高自旋一价锰（Mn(I)）中心上发生氮气活化的罕见实例。尽管由此可与镁的同类体系的观测结果建立若干富有启发性的类比，但由于相应一价锰中间体具备填满的d轨道，其与苯的反应行为呈现出显著差异：苯在此过程中发生了氧化加成（oxidative addition）。