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The molecular and electronic structure of edge-sharing bioctahedral [N(n-Bu)4]3[Re2(mnt)5] is reported here. Despite the short intermetal bond length of 2.6654(2) Å with computed bond order of 1.2, the unpaired electron is localised by the asymmetric ligand distribution, as demonstrated by its remarkable EPR spectrum.

Graphical abstract: Unprecedented spin localisation in a metal–metal bonded dirhenium complex

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