259881-87-3Relevant academic research and scientific papers
Intermolecular alkynyl ligand transfer in palladium(II) and platinum(II) complexes with -C≡CCOOR and -C≡CPh ligands. Relative stability of the alkynyl complexes and conproportionation of dialkynyl and diiodo complexes of these metals
Osakada, Kohtaro,Hamada, Makiko,Yamamoto, Takakazu
, p. 458 - 468 (2000)
An equimolar reaction of trans-Pd(C≡CCOOMe)2(PEt3)2 with trans-PdI2(PEt3)2 catalyzed by CuI causes conproportionation of the complexes at room temperature, producing trans-PdI(C≡COOMe)(PEt3)2 in 88% yield, while the reaction without CuI catalyst gives the monoalkynylpalladium complex in approximately 2% yield after a prolonged period. Similar reactions of trans-Pd(C≡CPh)2(PEt3)2 with trans-PdI2(PEt3)2 with and without CuI catalyst give the alkynyl ligand transfer reaction product trans-PdI(C≡CPh)(PEt3)2 in 95% and 33% yields, respectively. CuI-catalyzed conproportionation of trans-Pt(C≡CPh)2(PEt3)2 and trans-PtI2(PEt3)2 occurs more slowly than the corresponding reactions of the Pd complexes; trans-Pt(C≡CCOOMe)2(PEt3)2 does not react with the diiodoplatinum complex even in the presence of CuI. The alkynyl ligand transfer reaction from trans-Pd(C≡CCOOMe)2(PEt3)2 to trans-PtI2(PEt3)2 occurs in the presence of CuI catalyst, affording a mixture of several organopalladium and -platinum complexes. The main Pd complex in the reaction mixture is trans-PdI(C≡CCOOMe)(PEt3)2, while the Pt-containing product is composed of trans-Pt (C≡CCOOMe)2(PEt3)2, trans-PtI(C≡CCOOMe)(PEt3)2, and trans-PtI2(PEt3)2 in an approximate 1:2:1 molar ratio. Mixing of trans-Pd(C≡CCOOMe)2(PEt3)2, trans-PdI2(PEt3)2, and trans-PtI2(PEt3)2 results in the formation of trans-PdI(C≡CCOOMe)(PEt3)2 in a high yield, while the alkynyl ligand transfer from Pd to Pt complexes is almost negligible. trans-PtI2-(PEt3)2 catalyzes the alkynyl ligand transfer between the dialkynyl- and diiodopalladium-(II) complexes and remains unchanged in the reaction mixture.
