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The reaction of the bis(pentalene)dititanium complex Ti2(μ:η55-Pn)2 (Pn = C8H4(1,4-SiiPr3)2) with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene results in intramolecular C–H activation of one of the iPr methyl groups of a Pn ligand and formation of a “tucked-in” bridging hydride complex. The “tuck-in” process is reversed by the addition of hydrogen, which yields a dihydride featuring terminal and bridging hydrides.

Graphical abstract: C–H and H–H activation at a di-titanium centre

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