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Iridium Bis(phosphinite) p-XPCP Pincer Complexes:  Highly Active Catalysts for the Transfer Dehydrogenation of Alkanes

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posted on 18.02.2004, 00:00 by Inigo Göttker-Schnetmann, Peter White, Maurice Brookhart
A series of new bis(phosphinite) p-XPCPIrHCl pincer complexes {[PCP = η3-5-X−C6H2[OP(tBu)2]2-1,3], X = MeO (4a), Me (4b), H (4c), F (4d), C6F5 (4e), and ArF [=3,5-bis(trifluoromethyl)phenyl] (4f)} have been synthesized. Treatment of compounds 4af with NatOBu in cyclooctane (COA)/tert-butylethylene (TBE) mixtures generates species with unprecedented catalytic activity for the catalyzed transfer dehydrogenation of COA with TBE as acceptor to form cyclooctene (COE) and tert-butylethane (TBA). With substrate:precatalyst ratios of 3030COA:3030TBE:1p-XPCPIrHCl (4):1.1NaOtBu, turnover numbers (TONs) between 1400 and 2200 (up to 72% conversion in TBE) and initial turnover frequencies (TOFs) between 1.6 and 2.4 s-1 have been observed at 200 °C.

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