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N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand
Author(s) -
Hatzis Gillian P.,
Oliemuller Leah K.,
Dickie Diane A.,
Thomas Christine M.
Publication year - 2020
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.202000390
Subject(s) - chemistry , rhodium , thiophenol , dimer , ligand (biochemistry) , pincer ligand , pincer movement , stereochemistry , medicinal chemistry , catalysis , organic chemistry , receptor , biochemistry
The diphosphine, N‐heterocyclic phosphenium/phosphido (NHP + )/(NHP – )‐containing ligand (PPP +/– ) has been coordinated to rhodium to study the coordination chemistry of group 9 metals and NHP +/– fragments. Addition of the chlorophosphine ligand PP Cl P to [Rh(COD)Cl] 2 produces the complex (PP Cl P)RhCl ( 2 ), which can be reduced to form (PPP)Rh(PMePh 2 ) ( 3 ), the asymmetric dimer [(PPP)Rh] 2 ( 4 ), and the asymmetric dimer [(PPP)Rh(CN t Bu)] 2 ( 5 ). Analysis of the solid‐state structures and computational studies have provided insight into the electronic structure and bonding in 3–5 , revealing that the NHP +/– fragments in 3, 4 , and 5 are best described using an NHP – /Rh I description. Both 3 and 5 were found to be reactive towards the S–H bond of thiophenol, generating (PPP)RhSPh ( 6 ) and (PPP)Rh(SPh)(CN t Bu) ( 7 ), respectively.