Insights into the composition and structural chemistry of gallium(I) triflate

Josef Boronski; Matthew Stevens; Bono van IJzendoorn; Adrian C. Whitwood; John Martin Slattery

doi:10.1002/anie.202010837

Insights into the composition and structural chemistry of gallium(I) triflate

Josef Boronski, Matthew Stevens, Bono van IJzendoorn, Adrian C. Whitwood, John Martin Slattery

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

“GaOTf” is a simple, convenient source of low-valent gallium for synthetic chemistry and catalysis. However, little is currently known about its composition or reactivity. In this work, 71Ga NMR shows the presence of [Ga(arene)n]+ salts on oxidation of Ga metal with AgOTf in arene solvents. However, a more complex picture of speciation is uncovered by X-ray diffraction studies. In all cases, mixed-valence compounds containing Ga-arene and Ga-OTf coordination motifs, in addition to an unusual “naked” [Ga]+ ion, are found. Addition of 18-crown-6 allows for the isolation of a discrete Ga(I) crown complex. Evidence of a potential intermediate in the formation of “GaOTf” has been isolated in the form of the bimetallic silver(I)/gallium(I) cluster anion [Ag4{Ga(OTf)3}4(µ-Ga)6(OTf)4]2-.

Original language	English
Journal	Angewandte Chemie International Edition
Early online date	6 Oct 2020
DOIs	https://doi.org/10.1002/anie.202010837
Publication status	E-pub ahead of print - 6 Oct 2020

Bibliographical note

This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

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10.1002/anie.202010837

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John Martin Slattery
- john.slatteryyork.acuk
- Chemistry - Reader
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title = "Insights into the composition and structural chemistry of gallium(I) triflate",

abstract = "“GaOTf” is a simple, convenient source of low-valent gallium for synthetic chemistry and catalysis. However, little is currently known about its composition or reactivity. In this work, 71Ga NMR shows the presence of [Ga(arene)n]+ salts on oxidation of Ga metal with AgOTf in arene solvents. However, a more complex picture of speciation is uncovered by X-ray diffraction studies. In all cases, mixed-valence compounds containing Ga-arene and Ga-OTf coordination motifs, in addition to an unusual “naked” [Ga]+ ion, are found. Addition of 18-crown-6 allows for the isolation of a discrete Ga(I) crown complex. Evidence of a potential intermediate in the formation of “GaOTf” has been isolated in the form of the bimetallic silver(I)/gallium(I) cluster anion [Ag4{Ga(OTf)3}4(µ-Ga)6(OTf)4]2-.",

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AU - Slattery, John Martin

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AB - “GaOTf” is a simple, convenient source of low-valent gallium for synthetic chemistry and catalysis. However, little is currently known about its composition or reactivity. In this work, 71Ga NMR shows the presence of [Ga(arene)n]+ salts on oxidation of Ga metal with AgOTf in arene solvents. However, a more complex picture of speciation is uncovered by X-ray diffraction studies. In all cases, mixed-valence compounds containing Ga-arene and Ga-OTf coordination motifs, in addition to an unusual “naked” [Ga]+ ion, are found. Addition of 18-crown-6 allows for the isolation of a discrete Ga(I) crown complex. Evidence of a potential intermediate in the formation of “GaOTf” has been isolated in the form of the bimetallic silver(I)/gallium(I) cluster anion [Ag4{Ga(OTf)3}4(µ-Ga)6(OTf)4]2-.

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Insights into the composition and structural chemistry of gallium(I) triflate

Abstract

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John Martin Slattery

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