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Phosphine‐NHC Manganese Hydrogenation Catalyst Exhibiting a Non‐Classical Metal‐Ligand Cooperative H 2 Activation Mode
Author(s) -
Buhaibeh Ruqaya,
Filippov Oleg A.,
BruneauVoisine Antoine,
Willot Jérémy,
Duhayon Carine,
Valyaev Dmitry A.,
Lugan Noël,
Canac Yves,
Sortais JeanBaptiste
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901169
Subject(s) - phosphine , deprotonation , phosphonium , chemistry , catalysis , medicinal chemistry , ligand (biochemistry) , hydride , manganese , metal , valence (chemistry) , ylide , ketone , stereochemistry , inorganic chemistry , polymer chemistry , organic chemistry , ion , biochemistry , receptor
Deprotonation of the Mn I NHC‐phosphine complex fac‐[MnBr(CO) 3 (κ 2 P,C‐Ph 2 PCH 2 NHC)] ( 2 ) under a H 2 atmosphere readily gives the hydride fac‐[MnH(CO) 3 (κ 2 P,C‐Ph 2 PCH 2 NHC)] ( 3 ) via the intermediacy of the highly reactive 18‐e NHC‐phosphinomethanide complex fac‐[Mn(CO) 3 (κ 3 P,C,C‐Ph 2 PCHNHC)] ( 6 a ). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16‐e mangana‐substituted phosphonium ylide complex fac‐[Mn(CO) 3 (κ 2 P,C‐Ph 2 P=CHNHC)] ( 6 b ) as key intermediate able to activate H 2 via a non‐classical mode of metal‐ligand cooperation implying a formal λ 5 ‐P–λ 3 ‐P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre‐catalysts for ketone hydrogenation in the Mn I series reported to date (TON up to 6200).