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Heterobimetallic Carbene Complexes Bearing Cyclometalated Ir III /Rh III and Mixed NHC ∧ Py/PPh 3 Coordinated Pd II Centers: Structures and Tandem Catalysis
Author(s) -
Majumder Adhir,
Nath Saha Tarak,
Majumder Niladri,
Naskar Rajat,
Pal Kuntal,
Maity Ramananda
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202001080
Subject(s) - chemistry , carbene , catalysis , ligand (biochemistry) , pyridine , medicinal chemistry , transfer hydrogenation , tandem , yield (engineering) , stereochemistry , pincer movement , selectivity , organic chemistry , ruthenium , materials science , composite material , biochemistry , receptor , metallurgy
Heterobimetallic complexes bearing NHC donor ligands are gaining immense popularity in organometallic chemistry and tandem catalysis. It is known that the NHC reacts with Pd II in the presence of pyridine to yield PEPPSI type complexes and the NHC ligands having ortho‐C−H proton easily orthometalate to Ir III or Rh III centers. Combining these two methodologies in a stepwise fashion, we present here a series of heterobimetallic Ir III −Pd II and Rh III −Pd II complexes from a dicarbene donor ligand featuring cyclometalated Ir III or Rh III and mixedNHC ∧ Py /PPh 3 coordinated Pd II centers. All the heterobimetallic complexes have been structurally characterized by X‐ray crystallographic analysis. The heterobimetallic complexes featuring mixedNHC ∧ PPh 3coordinated Pd II centers show better activity in tandem Suzuki‐Miyaura/transfer hydrogenation reactions compared to both, the heterobimetallic complexes possessing PEPPSI type Pd II centers, and the equimolar mixture of their mononuclear Pd II and Rh III or Ir III counterparts. The heterobimetallic complex featuring cyclometalated Ir III and mixedNHC ∧ PPh 3coordinated Pd II center shows excellent selectivity for 4‐biphenylmethanol (isolated yield: 92 %) in tandem catalysis.