Synthesis and reactivity of aryl- and alkyl-palladium(II) complexes with functional phosphines and phosphinoenolate ligands: First analogues of model nickel catalysts

DOI: 10.1039/dt9960002903

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2903 - 2909 (1996)

Update date:2022-07-30

Topics:

Authors:

Andrieu, Jacques

Braunstein, Pierre

Naud, Frederic

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Article abstract of DOI:10.1039/dt9960002903

Phenyl- and methyl-palladium(II) complexes analogous to model nickel(II) catalysts were prepared from readily available precursors. The methods used allow different ligands to be introduced in the co-ordination sphere. For example, the chelating phosphinoenolate ligand in [PdPh{Ph₂PCH-^..C(-^..O)NPh₂}L ²] [L² = Ph₂PCH₂C(O)NPh₂] was displaced by 1 equivalent of Ph₂PCH₂C(O)Ph(L¹) to give [PdPh{Ph₂PCH-^..C(-^..O)Ph}L²] whereas the terminal functional phosphine was displaced by P(C₆H₁₁)₃ to give [PdPh{Ph₂PCH-^..C(-^..O)NPh₂}{P(C ₆H₁₁)₃}]. Owing to favourable ligand-redistribution reactions, treatment of a mixture of complexes trans-[PdMe(Cl)L²₂], trans-[PdMe(Cl)L¹₂] and trans-[PdMe(Cl)L¹(L²)] (which cannot be isolated pure) with an excess of NaOMe in toluene selectively afforded the phosphinoenolate complex [PdMe{Ph₂PCH-^..C(-^..)Ph}L²]. The enolate moiety of [PdPh{Ph₂PCH-^..C(-^..O)NPh₂}L ²] and of [PdMe{Ph₂PCH-^..C(-^..O)NPh₂}L ²] reacted with R′N=C=O (R′ = Ph or p-tolyl) with formation of a carbon-carbon bond in a Michael-type addition and the products were shown to exist in the form of two isomers a and b, characterised by a N-H ... O or a N-H ... N hydrogen bond within the ligand system. Insertion of CO into the Pd-Me bond of [PdMe{Ph₂PCH-^..C(-^..O)NPh₂}L ²] or [PdMe{Ph₂C[=C(O)NHPh]C(O)NPh₂}L²] yielded the corresponding acyl complexes. Although [PdMe{Ph₂PCH-^..C(-^..O)Ph}(PPh₃)] inserted ethylene into its Pd-Me bond, as evidenced by quantitative formation of propylene, the palladium hydride that must be generated by the β-elimination reaction decomposes before further ethylene insertion can occur.

Full text of DOI:10.1039/dt9960002903

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