Hydrogenolysis of the scorpionate-supported barium alkyl complex (Tp )Ba[CH(SiMe ) ](THF) (Tp =hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) afforded the dinuclear barium hydrido complex [(Tp )Ba(μ-H)] (2), which was characterized by NMR spectroscopy and single-crystal X-ray analysis. Exposure of 2 with 1 atm of CO resulted in a reductive coupling process to form the cis-ethendiolate dianion (3). Reaction of 2 with one equivalent of PhC≡C-C≡CPh gave barium 1,4-diphenyl-2-butyne-1,4-diyl complex {[(Tp )Ba] (PhCH-C≡C-CHPh) (4).
Mononuclear calcium unsubstituted alkyl complex [(TpAd,iPr)Ca{(CH2)4Ph}(THP)], proposed as the catalytic alkene hydrogenation intermediate, was isolated for the first time.
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