Synthesis, Structure, and Catalytic Activity of Cyclometalated Iridium Complexes with a Bidentate POC Ligand

Polukeev, Alexey V.Lund University,Lunds universitet,Centrum för analys och syntes,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Centre for Analysis and Synthesis,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH (author)

Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl (1 a) and (POC)(COD)IrHCl (1 b), from which complexes (POC)(L)IrHCl where L=PPh3 (1 c), bipyridine (1 d) and [2,2′-bipyridine]-6,6′-diol (1 e) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to dimeric complex [(POC)(bipy-diol−)IrH]2 (3) that could explain the low activity of 1 e. DFT studies provided insight into POC-H vs POCOP-H metalation mechanism.

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NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Inorganic Chemis ...

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