Proton-catalyzed hydrogenation of a d8 Ir(I) complex yields a trans Ir(III) dihydride

Michael Findlater, Wesley H. Bernskoetter, Maurice Brookhart

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65 Scopus citations


Hydrogenation of the (PONOP)Ir(I)CH3 complex [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] yields the unexpected trans-dihydride species (PONOP)IrCH3(H)2. Mechanistic investigations have revealed that this reaction proceeds via proton-catalyzed H2 cleavage, a pathway that circumvents the intermediacy of the typically invoked cis-dihydride isomer. Protonation yields the cationic (PONOP)Ir(CH 3)(H)+ complex, which is then trapped by H2 to yield an η2-H2 complex. Deprotonation of this species yields the trans-dihydride. Intermediates in the proposed pathway have been confirmed by independent low-temperature syntheses and spectroscopic observations.

Original languageEnglish
Pages (from-to)4534-4535
Number of pages2
JournalJournal of the American Chemical Society
Issue number13
StatePublished - Apr 7 2010


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