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Diborane and Triborane Species in the Coordination Sphere of Group‑8 Transition Metals

Pradhan, Alaka Nanda ; Bairagi, Subhash ; Ghosh, Sundargopal

Inorganic chemistry, 2023-09, Vol.62 (36), p.14790-14803 [Periódico revisado por pares]

American Chemical Society

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  • Título:
    Diborane and Triborane Species in the Coordination Sphere of Group‑8 Transition Metals
  • Autor: Pradhan, Alaka Nanda ; Bairagi, Subhash ; Ghosh, Sundargopal
  • É parte de: Inorganic chemistry, 2023-09, Vol.62 (36), p.14790-14803
  • Notas: ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: The synthesis and structural elucidation of a series of ruthenium diborane and triborane compounds are described. Treatment of [Cp*Ru­(PPh3)2Cl] (1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; PPh3 = triphenylphosphine) with [BH3·THF] (THF = tetrahydrofuran) at 60 °C led to the formation of the hydrogen-rich ruthena-octahydrotetraborane arachno-[2-{Cp*Ru­(PPh3)­B3H8}] (2). The chemistry of 2 is explored with [Fe2(CO)9] at room temperature, which resulted in the formation of a metal-stabilized triborane species, [{Cp*Ru­(PPh3)}­(μ3-η1:η2:η2-B3H6)­{Fe2(CO)7}] (3). Compound 3 can be considered as a triborane analogue [B3H6]3– that stabilizes in the coordination sphere of two iron and one ruthenium atoms. Further, the photolysis of nido-[1,2-(Cp*Ru)2(μ-H)2(B3H7)] (4) with [M­(CO)5·THF] (M = Mo and W) afforded an arachno-[1,2-(Cp*Ru)­(Cp*RuCO)­(μ-H)­(B3H8)] (5), in which the [M­(CO)5·THF] acted as a CO source. In an attempt to convert arachno-5 into a closo or nido species, we have pyrolyzed arachno-5 in toluene at 90 °C for 20 h that afforded nido-[2,3-(Cp*Ru)2(μ-CO)­(μ3-H)­(B3H6)] (6) having two ruthenium atoms at the basal position. Irradiation of arachno-5 with an intermediate generated from CS2 and [LiBH4·THF] in THF afforded the diborane(5) species [(Cp*RuCO)­(Cp*Ru)­(μ-H)­(μ-η1:η2-B2H4)­(CS2H)] (7) in which a dithioformato ligand (SHCS) is attached to one Ru–B bond. Compound 7 can be considered as a diborane(5) species, which is stabilized by a dithioformato ligand. All the synthesized compounds have been characterized by employing electrospray ionization-mass spectrometry, multinuclear NMR, and IR spectroscopy techniques. The single-crystal X-ray diffraction studies of compounds 2, 3, 6, and 7 helped to establish the structural integrity of these compounds. Further, density functional theory studies were performed to provide insight into the bonding of these metal-stabilized diborane and triborane species.
  • Editor: American Chemical Society
  • Idioma: Inglês
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