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

Alexa CaiseJoseph A B AbdallaRémi TirfoinAlison J EdwardsSimon Aldridge
Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2017)
Reactions of the β-diketiminate-stabilized gallium dihydride (Nacnac)Dipp GaH2 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)Dipp Ga 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 [L3 Ir(H)2 (H2 )]+ formulation and a formal IrIII oxidation state.
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