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

Michael Findlater; Wesley H. Bernskoetter; Maurice Brookhart

doi:10.1021/ja100168w

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

Michael Findlater, Wesley H. Bernskoetter, Maurice Brookhart

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

59 Scopus citations

Abstract

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 language	English
Pages (from-to)	4534-4535
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	132
Issue number	13
DOIs	https://doi.org/10.1021/ja100168w
State	Published - Apr 7 2010

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

abstract = "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.",

author = "Michael Findlater and Bernskoetter, {Wesley H.} and Maurice Brookhart",

year = "2010",

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T1 - Proton-catalyzed hydrogenation of a d8 Ir(I) complex yields a trans Ir(III) dihydride

AU - Findlater, Michael

AU - Bernskoetter, Wesley H.

AU - Brookhart, Maurice

PY - 2010/4/7

Y1 - 2010/4/7

N2 - 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.

AB - 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.

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