SiNN-pincer iridium complexes were synthesised and demonstrated to catalyse deuteration of trialkylsilanes with benzene-d6 through H/D exchange at room temperature.
16-Electron iridium complexes bearing a silyl-1,8-naphthyridine-based
bidentate ligand (napySi), Ir(κ2
Si,N-napySi)(H)(coe)X [X = Cl (1) and
Me (2)], were synthesized and characterized. Single-crystal
X-ray diffraction studies revealed that both 1 and 2 have a square-pyramidal geometry with the silyl moiety occupying
the apical position and the nitrogen lone pair of napySi adjacent
to the vacant metal center. Methyl complex 2 catalyzed
hydrogenation of alkenes with H2 (1 atm) at room temperature.
This hydrogenation proceeded significantly faster than that catalyzed
by a related complex with no nitrogen lone pair adjacent to the metal.
Based on this result, we suggest a possible catalytic cycle including
cooperative activation of H2 between the nitrogen lone
pair and the metal center for this system.
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