Preparation, characterization and reactivity of trifluoromethoxy palladium(ii) complexes†
Abstract
The preparation of the first nitrogen- or phosphine-ligated trifluoromethoxylated Pd(II) complexes [(L)Pd(4-CF3Ph)(OCF3)] (L = TMEDA, 4-mepyridine or tBu-BrettPhos, BrettPhos, RuPhos and CPhos) was described. These complexes were extensively characterized in the solid state and in solution, and the structures of the complexes were further confirmed by high resolution X-ray crystallography of the single crystals of complexes 2a/b and 5a. Thermolysis of complexes [(L)Pd(4-CF3Ph)(OCF3)] (tBu-BrettPhos, BrettPhos, RuPhos and CPhos) were explored but failed to give ArOCF3. DFT calculations showed that the barrier for a concerted Ar-OCF3 bond-forming reductive elimination from [(aryl)Pd(OCF3)] complexes 5 is much higher than that of the competitive β-fluorine elimination process.