Synthesis of the bulky phosphanide [P(SiiPr3)2]− and its stabilisation of low-coordinate Group 12 complexes
Publication Date
July 29, 2024
Description
Here, we report the first practical synthesis of the bulky phosphanide anion [P(SiiPr3)2]− in synthetically useful yields, and its complexation to Group 12 metals. The ligand is obtained as the sodium salt NaP(SiiPr3)2 1 in a 42% isolated yield and a single step from red phosphorus and sodium. This is a significant improvement on the previously reported synthesis of this ligand, and we have thus applied 1 to the synthesis of the two-coordinate complexes M[P(SiiPr3)2]2 (M = Zn, Cd, Hg). These Group 12 complexes are all monomeric and with non-linear P–M–P angles in the solid state, with DFT calculations suggesting that this bending is due to the steric demands of the ligand. Multinuclear NMR spectroscopy revealed complex 2nd order splitting patterns due to strong PP’ coupling. This work demonstrates that the synthesis of 1 is viable and provides a springboard for the synthesis of low-coordinate d-block complexes featuring this unusual bulky ligand.
Subjects (LCSH)
Subjects
Subjects (JACS)
Subjects (LC)
Divisions
University of Nottingham, UK Campus::Faculty of Science::School of Chemistry
University of Nottingham, UK Campus::Faculty of Engineering::Department of Chemical and Environmental Engineering
Data type
Experimental data: NMR spectra, mass spectrometry, IR spectra, crystallographic data, computational calculation outputs
Funders
Leverhulme Trust
Grant Number
EP/R004064/1
EP/S023909/1
RPG-2021-183
Data collection method
See metadata in upload
Resource languages
English
Publisher
University of Nottingham
Date Issued
January 25, 2025
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