Details

Autor(en) / Beteiligte

• Sharninghausen, Liam S.
• Sinha, Shashi Bhushan
• Shopov, Dimitar Y.
• Mercado, Brandon Q.
• Balcells, David
• Brudvig, Gary W.
• Crabtree, Robert H.

Titel

Synthesis and Characterization of Iridium(V) Coordination Complexes With an N,O‐Donor Organic Ligand

Ist Teil von

• Angewandte Chemie, 2017-10, Vol.129 (42), p.13227-13231

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2017

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• We have prepared and fully characterized two isomers of [IrIV(dpyp)2] (dpyp=meso‐2,4‐di(2‐pyridinyl)‐2,4‐pentanediolate). These complexes can cleanly oxidize to [IrV(dpyp)2]+, which to our knowledge represent the first mononuclear coordination complexes of IrV in an N,O‐donor environment. One isomer has been fully characterized in the IrV state, including by X‐ray crystallography, XPS, and DFT calculations, all of which confirm metal‐centered oxidation. The unprecedented stability of these IrV complexes is ascribed to the exceptional donor strength of the ligands, their resistance to oxidative degradation, and the presence of four highly donor alkoxide groups in a plane, which breaks the degeneracy of the d‐orbitals and favors oxidation. Ein robuster Ligand und ein seltener Oxidationszustand: [IrIV(dpyp)2] oxidiert glatt zu [IrV(dpyp)2]+, dem ersten einkernigen Kompex von IrV in einer N,O‐Donorumgebung. Die vollständige Charakterisierung der IrV‐Spezies, in einem Fall auch durch Röntgenkristallographie, gestattet die Erforschung dieses seltenen Oxidationszustands.