A Molecular Barium Hydrido Complex Stabilized by a Super‐Bulky Hydrotris(pyrazolyl)borate Ligand. Issue 52 (5th December 2017)

• Record Type: Journal Article
• Authors: Shi, Xianghui; Hou, Cuiping; Zhou, Chulu; Song, Yanyao; Cheng, Jianhua
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 52(2017)
• Page Start: 16650
• Page End: 16653
• Publication Date: 2017-12-05
• Subjects: alkaline-earth metals -- barium hydride -- butadiyne -- carbon monoxide -- tris(pyrazolyl)borate; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201709344
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hydrogenolysis of the scorpionate‐supported barium alkyl complex (Tp Ad, iPr )Ba[CH(SiMe3 )2 ](THF) (Tp Ad, iPr =hydrotris(3‐adamantyl‐5‐isopropyl‐pyrazolyl)borate) afforded the dinuclear barium hydrido complex [(Tp Ad, iPr )Ba(μ‐H)]2 (2 ), which was characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Exposure of2 with 1 atm of CO resulted in a reductive coupling process to form the cis‐ethendiolate dianion (3 ). Reaction of2 with one equivalent of PhC≡C−C≡CPh gave barium 1, 4‐diphenyl‐2‐butyne‐1, 4‐diyl complex {[(Tp Ad, iPr )Ba]2 (PhCH−C≡C−CHPh) (4 ). Abstract : Hydrides in a pinch : A barium hydride complex [(Tp Ad, i Pr )Ba( μ ‐H)]2 was obtained by the hydrogenolysis of (Tp Ad, i Pr )Ba[CH(SiMe3 )2 ](THF). The steric demand of the super bulky hydrotris(3‐adamantyl‐5‐isopropyl‐pyrazolyl)borate ligand (Tp Ad, i Pr ) is sufficient to stabilize the dimer. Reactions with diyne and CO indicate a rich chemistry for this complex.