Cooperative Rare‐Earth/Lithium‐Mediated Conversion of White Phosphorus

Abstract

AbstractThe rare‐earth/lithium cooperative effect on functionalization of white phosphorus has been investigated. The reaction of diazabutadiene‐supported yttrium hydride chelated a LiPPh2 molecule (LY ⋅ THF)2(μ‐H)2[μ‐PPh2(Li)] (1, L=N,N’‐di(2,6‐diisopropylphenyl)‐1,4‐diazabutadiene) with P4 gave two novel mixed Y/Li multinuclear polyphosphorus complexes (LY ⋅ THF)2[cyclo‐P3]Li(THF)3 (2) and [Li(THF)4]+[(LY ⋅ THF)3(norborane‐P7)Li(THF)]− (3), accompanied with the elimination of diphosphorus compound Ph2PPPh2 (4) and H2. However, the comparative reaction of yttrium hydride (LY ⋅ THF)2(μ‐H)2 with P4 afforded a trinuclear yttrium pyramid‐P4 complex (LY ⋅ THF)3(μ3‐P(PH)3) (5). Further investigations show that 5 cannot continuously react with LiPPh2 to form 2 and 3, and LiPPh2 reacted with P4 to form a Zintl‐P7 lithium complex (TMEDA⋅Li)3(Zintl‐P7) (6) and 4. These results indicated that the cooperation of Y/Li for activation of P4 is a key for the formation of 2 and 3. All new compounds have been characterized by NMR spectroscopy and single‐crystal X‐ray diffraction studies.