Dynamic Copper(I) and Silver(I) Complexes of Tri‐tert‐butyl‐cyclotriphosphane

In plain language

This research explores the synthesis and behaviour of new metal complexes formed by reacting tri-tert-butyl-cyclotriphosphane with copper(I) and silver(I) salts. The reactions yielded both dinuclear and tetranuclear coordination complexes containing either copper or silver centres linked by the cyclic phosphorus ligands. The resulting materials were isolated as crystalline powders or single crystals and structurally characterised using X-ray diffraction techniques. When dissolved in solution, the complexes display dynamic behaviour characterised by the continuous breaking and reforming of phosphorus-metal bonds. This process generates transient isomeric intermediates. Low-temperature phosphorus nuclear magnetic resonance spectroscopy revealed these dynamic solution-state equilibria, and the experimental conclusions were further validated through density functional theory calculations.

Key takeaways

Reactions of tri-tert-butyl-cyclotriphosphane with copper(I) and silver(I) salts yield dinuclear and tetranuclear complexes.
The resulting complexes were isolated as single crystals or crystalline powders and structurally confirmed by X-ray diffraction.
In solution, the compounds exhibit dynamic equilibria that involve continuous dissociation and reformation of metal-phosphorus bonds.
The dynamic isomeric processes were observed using low-temperature phosphorus NMR spectroscopy and supported by density functional theory calculations.

Why it matters

Understanding how metal-ligand bonds form, break, and rearrange in solution is fundamental to coordination chemistry. By revealing the dynamic equilibria of cyclic phosphorus ligands with copper and silver, this work offers precise structural and chemical insights into bond fluxionality, aiding the fundamental comprehension of organometallic molecule design and behaviour in solution.

Commercialisation angle

The abstract outlines fundamental early-stage coordination chemistry without testing or identifying any specific industrial use or translation pathway. Consequently, the abstract does not indicate an application pathway.

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Abstract

Abstract The reaction of cyclo‐(P3tBu3) with CuI and AgI salts led to the di‐ and tetranuclear complexes [Cun(μ‐Br)n{μ‐cyclo‐(P3tBu3)‐κP1,κP2}2] with n = 2 (1) and n = 4 (2) and [Agn(OTf)n(CH3CN)2n−2{μ‐cyclo‐(P3tBu3)‐κP1,κP2}2] with n = 2 (4) and n = 4 (5). Complexes 1, 2, 4 and 5 were isolated as crystalline powders or single crystals and characterized by X‐ray diffraction. In solution, these complexes exhibit a dynamic equilibrium which involves continuous dissociation and reforming of phosphorus−metal bonds leading to isomeric intermediates. This behavior was demonstrated by low‐temperature 31P{1H} NMR spectroscopy and the conclusions were corroborated by DFT calculations.

Research topics

Metal complexes synthesis and properties
Asymmetric Hydrogenation and Catalysis
Organometallic Complex Synthesis and Catalysis

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