TY - JOUR
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
N1 - Copyright:
Copyright 2010 Elsevier B.V., All rights reserved.
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.
UR - http://www.scopus.com/inward/record.url?scp=77950831831&partnerID=8YFLogxK
U2 - 10.1021/ja100168w
DO - 10.1021/ja100168w
M3 - Article
C2 - 20232913
AN - SCOPUS:77950831831
VL - 132
SP - 4534
EP - 4535
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 13
ER -