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

作者：Caise Alexa; Abdalla Joseph A B; Tirfoin Remi; Edwards Alison J; Aldridge Simon^*

来源：Chemistry - A European Journal, 2017, 23(66): 16906-16913.

DOI：10.1002/chem.201704372

• bond activation
• gallium
• hydrides
• iridium
• oxidative addition

Reactions of the beta-diketiminate-stabilized gallium dihydride (Nacnac)(GaH2)-Ga-Dipp with chelating Ir-I bis(phosphine) precursors under an H-2 atmosphere are shown to provide a simple route to IrV complexes stabilized by strongly sigma-donating hydrides and the carbene-like (Nacnac)Ga-Dipp donor. Characterization of these systems as seven-coordinate Ir-V tetrahydride species is supported by single crystal X-ray and neutron diffraction, and by T-1 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)(H-2)](+) formulation and a formal Ir-III oxidation state.

• 出版日期2017-11-27