Preparation and nuclear magnetic resonance spectra of bis(η3-allyl ylide)-, (η3-allyl)(η3-allyl ylide)-, (η3-allyl ylide)(η5-cyclopentadienyl ylide)-, and (η3-allyl)(η5-cyclopentadienyl ylide)-palladium(II) complexes

Abstract

Bis(η³-allyl ylide)palladium complexes with general formula [Pd{η³-(R¹₃P)CHCR²CHR³}{η³-(Ph₃P)CHCHCH₂}]-Y₂(1; R¹= Ph or Et; R²= H; R³= H or Me; Y = BF₄ or O₃SCF₃) are prepared by treating [Pd{η³-(R¹₃P)CHCR²CHR³}Cl₂] with AgY followed by addition of Ph₃PCH–CHCH₂. (η³-Allyl)(η³-allyl ylide)palladium complexes, [Pd(η³-CH₂CRCH₂){η³-(Ph₃P)CHCHCH₂}]Y (2: R = H or Me; Y = BF₄ or O₃SCF₃) are obtained similarly from the allylchloropalladium dimer. The series [Pd{η³-(R¹₃P)CHCHCHR²}{η⁵-(Ph₃P)C₅H₄}][BF₄]₂(3: R¹= Ph or Et; R²= H or Me) is prepared by the reaction of [Pd{η³-(R¹₃P)CHCHCHR²}Cl₂] with Ag[BF₄] and Ph₃P–C₅H₄. Treatment of [{Pd(η³-CH₂CR¹CR²R³)Cl}₂](R¹= H or Me; R²= H or Me; R³= H) with AgY (Y = BF₄ or O₃SCF₃) and Ph₃P–C₅H₄ gives [Pd(η³-CH₂CR¹CR²R³){η⁵-(Ph₃P)C₅H₄}]Y (4). The ¹H n.m.r. spectra of these new η³-allyl ylide and η⁵-cyclopentadienyl ylide palladium complexes are discussed.