Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

Xiaodan Chen; Zhongshu Li; Gernot Frenking; Israel Fernández; Lili Zhao; Hansjörg Grützmacher

doi:10.1002/chem.201900645

Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

Xiaodan Chen, Zhongshu Li, Gernot Frenking, Israel Fernández, Lili Zhao, Hansjörg Grützmacher

School of Chemistry and Moleculai Engineering

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	7912-7920
Number of pages	9
Journal	Chemistry - A European Journal
Volume	25
Issue number	33
DOIs	https://doi.org/10.1002/chem.201900645
State	Published - 12 Jun 2019

Keywords

allenes
bonding analysis
copper complexes
gold complexes
isonitriles
phosphorus

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10.1002/chem.201900645

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title = "Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands",

abstract = "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.",

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T1 - Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

AU - Chen, Xiaodan

AU - Li, Zhongshu

AU - Frenking, Gernot

AU - Fernández, Israel

AU - Zhao, Lili

AU - Grützmacher, Hansjörg

PY - 2019/6/12

Y1 - 2019/6/12

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AB - 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.

KW - allenes

KW - bonding analysis

KW - copper complexes

KW - gold complexes

KW - isonitriles

KW - phosphorus

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ER -

Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

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Keywords

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