Bis(trimethylsilyl)phosphide chemistry: a half-century of advances across the periodic table

Whilst bis(trimethylsilyl)amide has been used extensively as a ligand across the periodic table, the chemistry of its heavier group 15 congeners is relatively underdeveloped. However, bis(trimethylsilyl)phosphide coordination chemistry has provided unique structural motifs and has also shown potential applications in catalysis, materials science, and bioinorganic chemistry. This review, which marks 55 years since the first report of a bis(trimethylsilyl)phosphide complex, provides a comprehensive overview of the synthesis, characterisation and reactivity of structurally authenticated s-, p-, d- and f-block metal complexes of this ligand, focusing on salient single crystal XRD and NMR spectroscopic data. We discuss the factors influencing the diverse coordination modes and reactivity profiles of bis(trimethylsilyl)phosphide complexes, together with an overview of their potential as precursors for novel solid-state materials, aiming to inspire future research endeavours using this ligand. We also review the small number of bis(triisopropylsilyl)phosphide complexes, in order to provide motivation for the future study of other bis(silyl)phosphide ligands.