Synthese,Struktur und Reaktivität von Bis(dialkylamino)diphosphanen

Synthesis, Structure, and Reactivity of Bis(dialkylamino)diphosphines Starting with the aminochlorophosphines ⁱPr₂N? PCl₂ 1 and (ⁱPr₂N)₂P? Cl 2 , the synthesis of some new functionalized aminophosphines (ⁱPr₂N)₂P? SiMe₃ 3a , (ⁱPr₂N)₂P? SnMe₃ 3b , (ⁱPr₂N)(DMP)P? Cl 4 , ⁱPr₂N? P(SiMe₃)₂ 5 and ⁱPr₂N? P(SiMe₃)Cl 6 is reported. Reactions of 2 with different phosphides yield the aminodiphosphines (ⁱPr₂N)₂P? P(SiMe₃)₂ 7a , (ⁱPr₂N)₂P? P(SiMe₂^tBu)₂ 7b , (ⁱPr₂N)₂P? PPh₂ 8 and (ⁱPr₂N)₂P? PH₂ 9 . The phosphines 3a/b react with halogenophosphines to the aminohalogenodiphosphines (ⁱPr₂N)₂P? PCl₂ 10 , (ⁱPr₂N)₂P? P^tBuCl 11 and (ⁱPr₂N)₂P? P(NⁱPr₂)Cl 12 . The ambivalente aminophosphine 6 gives the aminotrichlorodiphosphine Cl(ⁱPr₂N)P? PCl₂ 13 after condensation with PCl₃, while the reactions with the corresponding lithiumphosphides yield the aminosilyldiphosphines (ⁱPr₂N)(SiMe₃)P? P(SiMe₃)₂ 14a and (ⁱPr₂N)(SiMe₃)P? P(SiMe₂^tBu)₂ 14b . The aminochlorophosphines 2/4 are reductively coupled with magnesium leading to the symmetrically substituted tetraaminodiphosphines (ⁱPr₂N)₂P? P(ⁱPr₂N)₂ 15a and DMP(ⁱPr₂N)P? P(ⁱPr₂N)DMP 15b . The functionalized aminosilyldiphosphine 7a is treated with methanol to yield the diphosphine (ⁱPr₂N)₂P? PH(SiMe₃) 16 and gives the lithium phosphinophosphide (ⁱPr₂N)₂P? PLi(SiMe₃) 17 after metallation with n-BuLi. The compounds are characterized by their NMR and mass spectra and the ³¹P-NMR values of the diphosphines are discussed according to their substituents. The crystal structures of 7b, 8 and 15b showing significantly differing conformations are presented.     

Synthese und Reaktivität von Diphenylphosphanyltrimethylsilylamin Ph2PN(H)SiMe3

Synthesis and Reactivity of the Diphenylphosphanyltrimethylsilylamine Ph₂PN(H)SiMe₃ The trimethylsilyliminotriphenylphosphoran Ph₃P=NSiMe₃ ( 1 ) reacts with sodium in THF under cleavage of one P–C_phenyl bond leading to the P^III‐species [(THF)₃Na(Ph₂PNSiMe₃)] ( 2 ). Reaction with NH₄Br or hydrolysis with water gives the diphenylphosphanyltrimethylsilylamine Ph₂PN(H)SiMe₃ ( 3 ) and in low yields the oxidized byproduct [(THF)Na(OOPPh₂)]_n ( 4 ) that can be synthesised directly in high yields in the reaction of Ph₂POOH and NaH in THF. 3 was reacted with an equimolar amount of Zn{N(SiMe₃)₂}₂ to give [(Me₃Si)₂NZnPh₂PNSiMe₃]₂ ( 5 ). 3 reacts with caesium under phosphorus‐phosphorus bond formation in a reductive substituent coupling reaction to give [(THF)Cs₂{Ph(NSiMe₃)P}₂]_n ( 6 ) where phosphorus(III) is reduced to phosphorus(II). Phosphorus‐phosphorus bond formation to give (Ph₂PNSiMe₃)₂ ( 7 ) where the phosphorus(III) centres are oxidized to P^IV is observed in the reaction of 3 with n‐BuLi and bismuthtrichloride.