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Updated: Aug 14, 2025
Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Cooperative Rare-Earth/Lithium-Mediated Conversion of White Phosphorus
Qing You1, Jie Zhang1, Fangjun Zhang1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Handan Road No 220, Shanghai, 200433, P. R. China.
Abstract:
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 (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 Ph2 PPPh2 (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.
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