Facile Activation of Dihydrogen by an Unsaturated Heavier Main Group Compound
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- 16 August 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (35) , 12232-12233
- https://doi.org/10.1021/ja053247a
Abstract
The germanium alkyne analogue Ar‘GeGeAr‘ (1, Ar‘ = C6H3-2,6(C6H3-2,6-Pri2)2) reacts with 1, 2, or 3 equiv of dihydrogen at room temperature, and at 1 atm pressure, to afford a mixture of the products Ar‘HGeGeHAr‘ (2), Ar‘H2GeGeH2Ar‘ (3), or Ar‘GeH3 (4). The relative amounts of each product are governed by the number of equivalents of hydrogen used. A mechanism for the initial step in the reaction is proposed. The appearance of 4 among the reaction products was accounted for in terms of either its dissociation to monomers or isomerization to the bridged Ar‘Ge(μ-H)2GeAr‘. The reactions were monitored by 1H NMR spectroscopy. The products 2, 3, and 4 were characterized by X-ray crystallography, and 4 was synthesized independently by the reduction of Ar‘Ge(OMe)3. These reactions represent the first direct addition of hydrogen to a closed shell unsaturated main group compound under ambient conditions.Keywords
This publication has 20 references indexed in Scilit:
- Reactivity of Ar‘GeGeAr‘ (Ar‘ = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) toward Alkynes: Isolation of a Stable DigermacyclobutadieneJournal of the American Chemical Society, 2004
- Germanium and Tin Analogues of Alkynes and Their Reduction ProductsJournal of the American Chemical Society, 2003
- Structural motifs and reactivity of small molecules containing subvalent Group 13 elements: matrix isolation and quantum chemical studiesDalton Transactions, 2003
- Probing the Reactivity of Aluminum(I) Compounds: The Reaction of Pentamethylcyclopentadienyl-Aluminum, Al[C5(CH3)5], Monomers with Dihydrogen in a Solid Ar Matrix to Give the New Aluminum Hydride Molecule H2Al[C5(CH3)5]Organometallics, 2002
- Synthesis and Structures of Germanium(II) Fluorides and HydridesOrganometallics, 2001
- Stabilized Terphenyl-Substituted Digermene Derivatives of Simple Organic Groups and Their Halide Precursors: Preference for Symmetrically Bonded StructuresOrganometallics, 2001
- [2,6-Trip2H3C6Sn(μ-H)]2 (Trip = C6H2-2,4,6-i-Pr3): Synthesis and Structure of a Divalent Group 14 Element HydrideJournal of the American Chemical Society, 2000
- Coordination chemistry of dihydrogenChemical Reviews, 1993
- Cryogenic reactions of gallium with molecular hydrogen and methaneInorganic Chemistry, 1993
- Singly bridged arrangements on Group 14 X2H4 potential surfacesJournal of the American Chemical Society, 1991