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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

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Molecular Calcium Phosphides and Mixed Phosphide Hydrides.

Kyle G Pearce¹, Luke Teh¹, Andrew S S Wilson¹

¹Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.

Inorganic Chemistry

|December 24, 2025

Summary

This study synthesized novel calcium phosphide derivatives using a bis(dihydroilido) ligand. These compounds exhibit unique bridging modes and potential, albeit marginal, catalytic activity for phosphine additions.

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Last Updated: Jan 7, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Published on: March 24, 2018

Area of Science:

Organometallic Chemistry
Calcium Chemistry
Coordination Chemistry

Background:

The synthesis of low-valent main group element compounds is crucial for understanding fundamental bonding and reactivity.
Calcium compounds, particularly those with bulky ligands, offer unique coordination environments and reactivity profiles.
Phosphido ligands are versatile building blocks in organometallic chemistry, enabling diverse synthetic transformations.

Purpose of the Study:

To synthesize novel diorganophosphido- and bis(trimethylsilyl)phosphidocalcium derivatives.
To investigate the structural diversity and bridging modes of these calcium phosphide compounds.
To explore the reactivity and potential catalytic applications of these new calcium complexes.

Main Methods:

Synthesis of calcium phosphide derivatives from a bis(dihydroilido)calcium hydride precursor.
Reaction with diphenylphosphine (Ph2PH) to form bridging phosphido complexes.
Transmetalation reactions with mercury phosphides (Hg(PR2)2) to introduce different phosphido ligands.
Reactions with unsaturated substrates and organometallic reagents to probe reactivity.

Main Results:

[(BDI)Ca-μ-PPh2]2 was synthesized, displaying differentiated phosphide bridging modes.
Selective replacement of one hydride in [(BDI)Ca-μ-H]2 was achieved via transmetalation with Hg(PR2)2 (R = t-Bu, SiMe3).
Heating [(BDI)Ca-μ-H]2 with P(SiMe3)3 yielded the labile [(BDI)Ca-μ-P(SiMe3)2]2, also with differentiated bridging modes.

Conclusions:

Novel calcium phosphide derivatives with unique structural features have been successfully synthesized.
The synthesized compounds exhibit interesting phosphide bridging modes, offering insights into calcium-phosphine interactions.
While showing some reactivity, the catalytic enhancement for phosphine additions is marginal compared to existing precatalysts.