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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.