Abstract
The oxidative addition reaction of Pd(PPh3)4 with Cl2CPN(SiMe3)2 forms the phosphavinyl phosphonium complex Cl(Ph3P)Pd[η2-C(Cl)(PPh3)PN(SiMe3)2] (IIIa), which results from PPh3 migration from Pd to carbon in the η1-phosphavinyl intermediate trans-Cl(Ph3P)2Pd[C(Cl)PN(SiMe3)2] (IIa). The reaction of Pd(dba)(dppe) with Cl2CPN(SiMe3)2 forms the η1-phosphavinyl complex cis-Cl(dppe)Pd[C(Cl)PN(SiMe3)2] (VI), which does not undergo phosphine migration. Compound IIIa undergoes substitution of the chloride ligand by PPh3 or MeCN in the presence of KPF6 to generate [(Ph3P)2Pd(η2-C(Cl)(PPh3)PN(SiMe3)2)](PF6) (IV) or [(Ph3P)(MeCN)Pd(η2-C(Cl)(PPh3)PN(SiMe3)2)](PF6) (V), respectively; the structure of V was determined by X-ray diffraction studies. The reaction of Pd(PEt3)4 with Cl2CPN(SiMe3)2 forms the η1-phosphavinyl complex trans-Cl(Et3P)2Pd[C(Cl)PN(SiMe3)2] (IIb), which does not undergo PEt3 migration. When 2 equiv of Pd(PEt3)4 are reacted with Cl2CPN(SiMe3)2 the phosphonio−methylene(imino)metallophosphorane complex ...
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