PH3 as a Phosphorus Source for Phosphinidene–Carbene Adducts and Phosphinidene–Transition Metal Complexes

Authors

  • Mark Bispinghoff Laboratory of Inorganic Chemistry, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093 Zürich, Switzerland. bispinghoff@inorg.chem.ethz.ch
  • Hansjörg Grützmacher Laboratory of Inorganic Chemistry, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093 Zürich, Switzerland

DOI:

https://doi.org/10.2533/chimia.2016.279

Keywords:

Carbene insertion, N-heterocyclic carbenes, Phosphine gas ph3, Phosphinidene complexes, Transition metal complexes

Abstract

The parent phosphinidene–carbene adduct NHC=PH is a versatile synthon in main group chemistry and can act as an electronically flexible ligand for transition metals. Previously, it could only be synthesized with sterically demanding N-aryl substituents. This paper describes simple methods for the synthesis of NHC=PH adducts with varying steric demand from elemental phosphorus or easily accessible phosphorus sources. Furthermore, the reactivity of NHCs towards PH3 was investigated. It was shown how a NHC inserts into the P–H bond of PH3, which opens up a route to NHC=PH adducts from an imidazolium salt and PH3. The adducts were used in the simple syntheses of bis(phosphinidene) mercury(II) and group 6 pentacarbonyl parent phosphinidene complexes. Their electronic and structural properties were investigated to elucidate the influence of the NHC on the phosphinidene and identify possible applications.

Downloads

Published

2016-04-27

How to Cite

[1]
M. Bispinghoff, H. Grützmacher, Chimia 2016, 70, 279, DOI: 10.2533/chimia.2016.279.