Publications Repository - Gdańsk University of Technology

Phospha-Wittig (phosphanylphosphinidene titanium(IV) complex) and phospha-Peterson (lithiated diphosphane) reactions were used to obtain phosphanylphosphaalkenes with the general formula XYC=P-PtBu2 (X = alkyl, aryl group or H; Y = alkyl or aryl group). Therefore, two series of reactions with different ketones and aldehydes were performed. An examination revealed that the two methods are complementary. For smaller carbonyl compounds, the phospha-Wittig reaction was shown to be a much better method, while for larger substituents (mainly aromatic), the phospha-Peterson reaction was shown to be a reliable method. These studies led to, among other things, the isolation of seven phosphanylphosphaalkenes in crystalline form after the phospha-Peterson reaction: (Ph)2C=P-PtBu2 (3a), Z-(Ph)(4-CN-Ph)C=P-PtBu2 (3c), (4-CN-Ph)2C=P-PtBu2 (3d), (4-MeO-Ph)2C=P-PtBu2 (3e), E-tBu(Ph)C=P-PtBu2 (3f), E-{(Me)2N-Ph}(H)C=P-PtBu2 (4d) and E-PhPh(H)C=P-PtBu2 (4e). Corresponding compounds were obtained at high yields under mild conditions, and more importantly, these new species are relatively air- and absolutely moisture-stable, especially these originating from aldehydes aldehyde. Additionally, a comprehensive DFT study helped us to establish not only the key factors crucial for the effective phospha-Wittig-based synthesis of C=P-P species but also the consecutive steps along the reaction path leading to the formation of these compounds.

Authors

• dr inż. Aleksandra Ziółkowska link open in new tab ,
• mgr inż. Natalia Szynkiewicz link open in new tab ,
• dr hab. inż. Łukasz Ponikiewski link open in new tab