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Sequential Double Dearomatization of the Pyrazolate‐Based “Two‐in‐One” Pincer Ligand in a Dinuclear Rhodium(I) Complex
Author(s) -
GersBarlag Alexander,
Goursot Pierre,
Li Ming,
Dechert Sebastian,
Meyer Franc
Publication year - 2019
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.201900477
Subject(s) - chemistry , deprotonation , rhodium , pincer movement , ligand (biochemistry) , pincer ligand , pyridine , stereochemistry , methylene , cryptand , medicinal chemistry , crystallography , organic chemistry , catalysis , ion , biochemistry , receptor
A binucleating pyrazolate‐based ligand providing two tridentate PNN compartments is shown to form a dinuclear rhodium(I) complex [L{Rh(CO)} 2 ](PF 6 ) ( 1 ) that can be deprotonated at both side arm methylene groups between pyridine and phosphino donors to give K[L**{Rh(CO)} 2 ] ( 3 ). Sequential twofold deprotonation has been monitored by NMR and UV/Vis spectroscopy and proceeds via the neutral intermediate L*{Rh(CO)} 2 ( 2 ). X‐ray crystallographic characterization of 1 and the K[2,2,2] + salt 3′ ([2,2,2] is a cryptand) evidences pyridine dearomatization upon deprotonation, and all spectroscopic and structural signatures are in good agreement with those of related mononuclear rhodium complexes based on a common PNN pincer ligand, which corroborates that pyrazolate‐bridged L – is best described as a scaffold with two pincer‐type subunits.