Synthesis of a High-Valent, Four-Coordinate Manganese Cubane Cluster with a Pendant Mn Atom: Photosystem II-Inspired Manganese–Nitrogen Clusters

Abstract

High-valent, four-coordinate manganese imido- and nitrido-bridged heterodicubane clusters have been prepared and characterized by single-crystal X-ray diffraction and spectroscopic techniques. The title compound, a corner-nitride-fused dicubane with the chemical formula [Mn₅Li₃(μ₆-N)­(N)­(μ₃-N^<i>t</i>Bu)₆(μ-N^<i>t</i>Bu)₃(N^<i>t</i>Bu)] (<b>1</b>), has been prepared as an adduct with a nearly isostructural tetramanganese cluster with one Mn atom replaced by Li. An important feature of the reported chemistry is the formation of nitride from <i>tert</i>-butylamide, indicative of N–C bond cleavage facilitated by manganese