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Characterization and Reactivity Studies of Dinuclear Iridium Hydride Complexes Prepared from Iridium Catalysts with N,P and C,N Ligands Under Hydrogenation Conditions

Gruber, Stefan and Neuburger, Markus and Pfaltz, Andreas. (2013) Characterization and Reactivity Studies of Dinuclear Iridium Hydride Complexes Prepared from Iridium Catalysts with N,P and C,N Ligands Under Hydrogenation Conditions. Organometallics, 32 (16). pp. 4702-4711.

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Official URL: http://edoc.unibas.ch/dok/A6212008

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Abstract

The dinuclear iridium hydride complexes [IrH(CH3CN)(L1)(μ-H)]2(BArF)2 (7; L1 = (S)-2-(2-((diphenylphosphanyl)oxy)propan-2-yl)-4-isopropyl-4,5-dihydrooxazole, BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), [IrH(CH2Cl2)(L1)(μ-H)]2(BArF)2 (8), [IrH(L2)(μ-H)]2(BArF)2 (9a; L2 = (S)-1-[2-(2-adamantan-2-yl-4,5-dihydrooxazol-4-yl)-ethyl]-3-(2,6-diisopropylphenyl)-1,2-dihydroimidazol-2-ylidene), and [IrH(L3)(μ-H)]2(BArF)2 (9b; L3 = (S)-1-[2-(2-tert-butyl-4,5-dihydrooxazol-4-yl)-ethyl]-3-(2,6-diisopropylphenyl)-1,2-dihydroimidazol-2-ylidene) were prepared from the corresponding mononuclear [Ir(COD)(L)]BArF precursors by treatment with H2 and characterized by 2D NMR spectroscopy and X-ray diffraction. Conversion to a trinuclear iridium hydride complex, which is usually observed for N,P iridium hydride complexes, is inhibited by addition of 0.5 equiv of [H(OEt2)2]BArF or acetonitrile. Reactions with acetonitrile or 6,6′-bi-2-picoline afforded the mononuclear iridium dihydride complexes [Ir(H)2(CH3CN)2(L1)]BArF (5), [Ir(H)2(CH3CN)2(L3)]BArF (10), or [Ir(H)2(6,6′-bi-2-picoline)(L3)]BArF (11). The CH3CN complexes 7 and 10 are inactive as hydrogenation catalysts. In contrast, the coordinatively unsaturated dinuclear complexes 9a and 9b are active catalysts for the hydrogenation of (E)-1,2-diphenyl-1-propene at 50 bar hydrogen pressure.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Synthetische organische Chemie (Pfaltz)
UniBasel Contributors:Pfaltz, Andreas and Neuburger, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0276-7333
e-ISSN:1520-6041
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:10 Apr 2017 08:52
Deposited On:31 Jan 2014 09:51

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