Iridium half-sandwich complexes with di- and tridentate bis(pyridylimino)isoindolato ligands: stoichiometric and catalytic reactivity
A series of κ2-(N,N)-coordinated bis(2-pyridylimino)isoindolato (BPI) complexes [Cp*Ir(BPI)Cl], which possess “three-legged piano-stool” structures, with the iridium atom being coordinated by the Cp* ligand 2 × N and Cl, were prepared via deprotonation of the BPIH ligands with either potassium hydri...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
January 15, 2015
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| In: |
Organometallics
Year: 2015, Volume: 34, Issue: 11, Pages: 2326-2342 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om501138t |
| Online Access: | Verlag, Volltext: https://doi.org/10.1021/om501138t
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| Author Notes: | Astrid L. Müller, Tim Bleith, Torsten Roth, Hubert Wadepohl, and Lutz H. Gade |
| Summary: | A series of κ2-(N,N)-coordinated bis(2-pyridylimino)isoindolato (BPI) complexes [Cp*Ir(BPI)Cl], which possess “three-legged piano-stool” structures, with the iridium atom being coordinated by the Cp* ligand 2 × N and Cl, were prepared via deprotonation of the BPIH ligands with either potassium hydride or LDA and subsequent reaction with [Cp*IrCl2]2 in THF. Cationic complexes [Cp*Ir(BPI)]+ containing κ3-(N,N,N)-coordinated BPI ligands were prepared as well as complexes with bidentate-coordinated BPI ligands, where the chloride ligand was substituted by either neutral or anionic ligands. Substitution in the ortho-position of the PBI ligands led to the formation of cycloiridated κ3-(N,N,C) species. Upon substitution of the anionic ligand by triphenylphosphine, a product was obtained with a hitherto unobserved κ2-(N,N) coordination of oMe-BPI to the metal center via the deprotonated nitrogen atom of the isoindole unit and one of the imine nitrogen atoms of the BPI ligand. A series of (para-cymene) osmium half-sandwich complexes with analogous structures and reactivities to their isoelectronic Cp*Ir(BPI) congeners were also prepared. Finally, it has been demonstrated that both Ir and Os complexes are catalytically active in the transfer hydrogenation of various ketones and imines. |
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| Item Description: | Gesehen am 20.07.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om501138t |