Formation of Gallium Monofluoride in the Coordination Sphere of Nickel
Abstract
Monovalent gallium halides are intrinsically unstable compounds at room temperature and can only be generated in the gas phase at temperatures of about 1000 degrees C. Although they are isoelectronic to carbon monoxide, dinitrogen, and the cyanide ion, which are pivotal ligands in coordination chemistry, monovalent gallium halides are largely unexplored as ligands with transition metals. Herein, we report the isolation of a dicationic nickel complex bearing a gallium monofluoride ligand. The +I oxidation state of the gallium centre is supported by NMR-spectroscopic methods, X-ray photoelectron spectroscopy, as well as density functional theory calculations. Analysis of the bonding situation between the GaF ligand and the central nickel atom suggests strong sigma-donating, but negligible pi-accepting properties for the supported GaF fragment. The GaF moiety forms as a product of C(sp3)-F bond activation of the weakly coordinating BArF24 (tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate) anion and serves as a fluorine source for silicon and carbon electrophiles. This leads to facile defluorination, forming the fluoride-free complex and fluorinated products such as fluorotrimethylsilane or benzoyl fluoride.
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BibTeX
@article{stephan2026formation,
title = {{Formation of Gallium Monofluoride in the Coordination Sphere of Nickel}},
author = {Johannes Stephan and Samia Kahlal and Jean-Yves Saillard and Marvin Muhlau and Lisa Gremmel and Christian Gemel and Roland A. Fischer},
journal = {Angewandte Chemie International Edition},
year = {2026},
month = aug,
doi = {10.1002/anie.1189853},
url = {https://hal.science/hal-05683550v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Formation of Gallium Monofluoride in the Coordination Sphere of Nickel
AU - Johannes Stephan
AU - Samia Kahlal
AU - Jean-Yves Saillard
AU - Marvin Muhlau
AU - Lisa Gremmel
AU - Christian Gemel
AU - Roland A. Fischer
PY - 2026
DA - 2026/08/17
JO - Angewandte Chemie International Edition
DO - 10.1002/anie.1189853
UR - https://hal.science/hal-05683550v1
AB - Monovalent gallium halides are intrinsically unstable compounds at room temperature and can only be generated in the gas phase at temperatures of about 1000 degrees C. Although they are isoelectronic to carbon monoxide, dinitrogen, and the cyanide ion, which are pivotal ligands in coordination chemistry, monovalent gallium halides are largely unexplored as ligands with transition metals. Herein, we report the isolation of a dicationic nickel complex bearing a gallium monofluoride ligand. The +I oxidation state of the gallium centre is supported by NMR-spectroscopic methods, X-ray photoelectron spectroscopy, as well as density functional theory calculations. Analysis of the bonding situation between the GaF ligand and the central nickel atom suggests strong sigma-donating, but negligible pi-accepting properties for the supported GaF fragment. The GaF moiety forms as a product of C(sp3)-F bond activation of the weakly coordinating BArF24 (tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate) anion and serves as a fluorine source for silicon and carbon electrophiles. This leads to facile defluorination, forming the fluoride-free complex and fluorinated products such as fluorotrimethylsilane or benzoyl fluoride.
SN - 1433-7851
SN - 1521-3773
ER -