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

Caise Alexa | Zendy; Abdalla Joseph A. B. | Zendy; Tirfoin Rémi | Zendy; Edwards Alison J. | Zendy; Aldridge Simon | Zendy

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

Author(s) -

Caise Alexa,

Abdalla Joseph A. B.,

Tirfoin Rémi,

Edwards Alison J.,

Aldridge Simon

Publication year - 2017

Publication title -

chemistry – a european journal

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.687

H-Index - 242

eISSN - 1521-3765

pISSN - 0947-6539

DOI - 10.1002/chem.201704372

Subject(s) - phosphine , hydride , oxidizing agent , chemistry , steric effects , gallium , infrared spectroscopy , single crystal , chelation , carbene , crystallography , oxidation state , medicinal chemistry , inorganic chemistry , stereochemistry , metal , organic chemistry , catalysis

Reactions of the β‐diketiminate‐stabilized gallium dihydride (Nacnac) Dipp GaH 2 with chelating Ir I bis(phosphine) precursors under an H 2 atmosphere are shown to provide a simple route to Ir V complexes stabilized by strongly σ‐donating hydrides and the carbene‐like (Nacnac) Dipp Ga 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 [L 3 Ir(H) 2 (H 2 )] + formulation and a formal Ir III oxidation state.

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