Details

Autor(en) / Beteiligte

• Caise, Alexa
• Abdalla, Joseph A. B.
• Tirfoin, Rémi
• Edwards, Alison J.
• Aldridge, Simon

Titel

A Gallium Hydride as an Oxidizing Agent: Direct Synthesis of IrV Complexes via Ga−H Bond Activation

Ist Teil von

• Chemistry : a European journal, 2017-11, Vol.23 (66), p.16906-16913

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2017

Link zum Volltext

Quelle

Wiley-Blackwell Full Collection

Beschreibungen/Notizen

• Reactions of the β‐diketiminate‐stabilized gallium dihydride (Nacnac)DippGaH2 with chelating IrI bis(phosphine) precursors under an H2 atmosphere are shown to provide a simple route to IrV complexes stabilized by strongly σ‐donating hydrides and the carbene‐like (Nacnac)DippGa donor. Characterization of these systems as seven‐coordinate IrV tetrahydride species is supported by single crystal X‐ray and neutron diffraction, and by T1 NMR measurements. By contrast related systems featuring more sterically demanding (non‐chelating) ancillary ligands are better described in terms of a bis(hydride) dihydrogen [L3Ir(H)2(H2)]+ formulation and a formal IrIII oxidation state. High‐five!: Reactions of (Nacnac)DippGaH2 with chelating IrI bis(phosphine) precursors provide a simple route to IrV complexes stabilized by strongly σ‐donating hydrides and the carbene‐like (Nacnac)DippGa donor. Related systems featuring more sterically demanding ancillary ligands, by contrast, are better described in terms of a bis(hydride) dihydrogen [Ir(H)2(H2)] formulation and a formal IrIII oxidation state.