The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl ...The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl group or H;Y=alkyl or aryl group).Therefore,two series of reactions with different ketones and aldehydes were performed.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)_(2)CvP-PtBu_(2)(3a),Z-(Ph)(4-CN-Ph)CvP-PtBu_(2)(3c),(4-CN-Ph)_(2)CvP-PtBu_(2)(3d),(4-MeO-Ph)_(2)CvP-PtBu_(2)(3e),E-tBu(Ph)CvP-PtBu_(2)(3f),E-{(Me)_(2)N-Ph}(H)CvP-PtBu_(2)(4d)and E-PhPh(H)CvP-PtBu_(2)(4e).The corresponding compounds were obtained in high yields under mild conditions,and more importantly,these new species are relatively air-and absolutely moisture-stable,especially those originating from aldehydes.In addition,a comprehensive DFT study helped us to establish not only the key factors crucial for effective phospha-Wittig-based synthesis of CvP-P species but also the consecutive steps along the reaction path leading to the formation of these compounds.展开更多
基金support for these studies from Gdańsk University of Technology by the DEC-8/2020/IDUB/I.3.3 grant under the Argentum-‘Excellence Initiative-Research University’program is gratefully acknowledged.Ł.P。
文摘The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl group or H;Y=alkyl or aryl group).Therefore,two series of reactions with different ketones and aldehydes were performed.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)_(2)CvP-PtBu_(2)(3a),Z-(Ph)(4-CN-Ph)CvP-PtBu_(2)(3c),(4-CN-Ph)_(2)CvP-PtBu_(2)(3d),(4-MeO-Ph)_(2)CvP-PtBu_(2)(3e),E-tBu(Ph)CvP-PtBu_(2)(3f),E-{(Me)_(2)N-Ph}(H)CvP-PtBu_(2)(4d)and E-PhPh(H)CvP-PtBu_(2)(4e).The corresponding compounds were obtained in high yields under mild conditions,and more importantly,these new species are relatively air-and absolutely moisture-stable,especially those originating from aldehydes.In addition,a comprehensive DFT study helped us to establish not only the key factors crucial for effective phospha-Wittig-based synthesis of CvP-P species but also the consecutive steps along the reaction path leading to the formation of these compounds.
