TY - JOUR
T1 - Insights into the Composition and Structural Chemistry of Gallium(I) Triflate
AU - Boronski, Josef
N1 - Funding Information:
We are grateful to the University of York and EPSRC (grants EP/H011455 and EP/K031589/1) for funding.
Publisher Copyright:
© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
PY - 2021/1/12
Y1 - 2021/1/12
N2 - “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 spectroscopy 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 GaI 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−.
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 spectroscopy 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 GaI 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−.
KW - X-ray crystallography
KW - coordination chemistry
KW - density functional calculations
KW - low-valent gallium
KW - main-group chemistry
U2 - 10.1002/anie.202010837
DO - 10.1002/anie.202010837
M3 - Article
C2 - 33022877
SN - 1433-7851
VL - 60
SP - 1567
EP - 1572
JO - Angewandte Chemie. International Edition
JF - Angewandte Chemie. International Edition
IS - 3
ER -