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

The 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)(mu-H)(2)[mu-PPh2(Li)] (1, L=N,N'-di(2,6-diisopropylphenyl)-1,4-diazabutadiene) with P-4 gave two novel mixed Y/Li multinuclear polyphosphorus complexes (LY . THF)(2)[cyclo-P-3]Li(THF)(3) (2) and [Li(THF)(4)](+)[(LY . THF)(3)(norborane-P-7)Li(THF)](-) (3), accompanied with the elimination of diphosphorus compound Ph2PPPh2 (4) and H-2. However, the comparative reaction of yttrium hydride (LY . THF)(2)(mu-H)(2) with P-4 afforded a trinuclear yttrium pyramid-P-4 complex (LY . THF)(3)(mu(3)-P(PH)(3)) (5). Further investigations show that 5 cannot continuously react with LiPPh2 to form 2 and 3, and LiPPh2 reacted with P-4 to form a Zintl-P-7 lithium complex (TMEDA.Li)(3)(Zintl-P-7) (6) and 4. These results indicated that the cooperation of Y/Li for activation of P-4 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.