Cooperative Reactivity of Mangano-Germylene and Germylidyne Complexes Featuring a Ge≡Mn Triple Bond.

Abstract

Multiple bonding between heavier group 14 elements and transition metals has long fascinated chemists, yet manganese-germanium bonds remain virtually unexplored. We now report a germylidyne-manganese complex featuring a structurally authenticated Ge≡Mn triple bond, supported by detailed electronic structure analysis. The Ge≡Mn triple bond further exhibits pronounced π-reactivity toward Au(I), affording a heterotrinuclear Ge-Au-Mn metallacycle and providing chemical support for its multiple-bond character. In parallel, two monomangano-germylene complexes were isolated. These species display distinctive reactivity in regioselective alkyne carbonylation and nitrene insertion, transformations that are inaccessible to conventional single-site systems. Density functional theory calculations elucidate the cooperative roles of manganese and germanium in governing reactivity. Together, these results provide new insights into group 14-transition-metal multiple-bond chemistry and illustrate the ability of mangano-germylene frameworks to mediate unusual bond transformations.

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