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Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands
Author(s) -
Chen Xiaodan,
Li Zhongshu,
Frenking Gernot,
Fernández Israel,
Zhao Lili,
Grützmacher Hansjörg
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900645
Subject(s) - lone pair , carbene , bent molecular geometry , reactivity (psychology) , chemistry , molecule , center (category theory) , electron pair , crystallography , carbon fibers , ligand (biochemistry) , stereochemistry , ion , electron , materials science , catalysis , organic chemistry , physics , medicine , alternative medicine , pathology , quantum mechanics , composite number , composite material , biochemistry , receptor
Phosphaheteroallenes R−P=C=L, with L = N‐heterocyclic carbenes (NHCs), can be viewed to a certain extent as phosphaisonitriles stabilized with NHCs, R−P=C:←L. The suitability of these molecules as ligands for coinage‐metal ions was investigated and coordination through the central carbon center was observed in most cases. A combination of experiments, spectroscopic methods, and DFT calculations indicates the presence of a hidden electron pair at the carbon center of R−P=C:←L. Remarkably, this lone pair also inserts intramolecularly in C−H bonds showing the carbene‐type reactivity which is expected for phosphaisonitriles.