The steric bulk of the phosphane ligand determines the mechanism of the ArX addition to zero-valent [PdL2] complexes. This effect has been studied by variation of ligands (catalyst: [Pd(PCxntBu3−n)2]; n=0–3, Cx=cyclohexyl) in Pd couplings of unsaturated electrophiles, and different reaction pathways (A=associative, B=dissociative) identified, depending on the size of the ligand.
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Galardon et al. (2002) studied this question.
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