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Updated: Jan 19, 2026
Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Synthesis, Structural Characterization, and Coordination Chemistry of (Trineopentylphosphine)palladium(aryl)bromide
Huaiyuan Hu1, Monica Vasiliu1, Trent H Stein1
1Department of Chemistry and Biochemistry , The University of Alabama , Box 870336, Tuscaloosa , Alabama 35487-0336 , United States.
Abstract:
A series of [(PNp3)Pd(Ar)Br]2 complexes (PNp3 = trineopentylphosphine, Ar = 4-tolyl, 4-tert-butylphenyl, 2-tolyl, 4-methoxy-2-methylphenyl, 2-isopropylphenyl, and 2,6-dimethylphenyl) were synthesized and structurally characterized by X-ray crystallography and density functional theory optimized structures. The trineopentylphosphine ligand is able to accommodate coordination of other sterically demanding ligands through changes in its conformation. These conformational changes can be seen in changes in percent buried volume of the PNp3 ligand. The binding equilibria of the [(PNp3)Pd(Ar)Br]2 complexes with pyridine derivatives were determined experimentally and analyzed computationally. The binding equilibria are sensitive to the steric demand of the pyridine ligand and less sensitive to the steric demand of the aryl ligand on palladium. In contrast to previous studies, the binding equilibria do not correlate with pyridine basicity. The binding equilibria results are relevant to fundamental ligand coordination steps in cross-coupling reactions, such as Buchwald-Hartwig aminations.
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