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 LiPPh 2 molecule (LY ⋅ THF) 2 (μ-H) 2 [μ-PPh 2 (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 Ph 2 PPPh 2 (4) and H 2 . However, the comparative reaction of yttrium hydride (LY ⋅ THF) 2 (μ-H) 2 with P 4 afforded a trinuclear yttrium pyramid-P 4 complex (LY ⋅ THF) 3 (μ 3 -P(PH) 3 ) (5). Further investigations show that 5 cannot continuously react with LiPPh 2 to form 2 and 3, and LiPPh 2 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.