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Reactive Dimerization of an N‐Heterocyclic Plumbylene: C−H Activation with Pb II
Author(s) -
Guthardt Robin,
Oetzel Jan,
Schweizer Julia I.,
Bruhn Clemens,
Langer Robert,
Maurer Martin,
Vícha Jan,
Shestakova Pavletta,
Holthausen Max C.,
Siemeling Ulrich
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.201811559
Subject(s) - electrophile , intramolecular force , chemistry , dimer , bond cleavage , cyclopentadienyl complex , cleavage (geology) , stereochemistry , medicinal chemistry , electrophilic substitution , electrophilic addition , catalysis , organic chemistry , materials science , fracture (geology) , composite material
The N‐heterocyclic plumbylene [Fe{(η 5 ‐C 5 H 4 )NSiMe 3 } 2 Pb:] is in equilibrium with an unprecedented dimer in solution, whose formation involves the cleavage of a strong C−H bond and concomitant formation of a Pb−C and an N−H bond. According to a mechanistic DFT assessment, dimer formation does not involve direct Pb II insertion into a cyclopentadienyl C−H bond, but is best described as an electrophilic substitution. The bulkier plumbylene [Fe{(η 5 ‐C 5 H 4 )NSitBuMe 2 } 2 Pb:] shows no dimerization, but compensates its electrophilicity by the formation of an intramolecular Fe−Pb bond.