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The phosphinoamide chemistry has attracted a considerable attention owing to the structural diversity of the associated complexes. To further understand the properties of the P-N bond, Ashby synthesized the compound [(Ph2P-NPh)Li(Et2O)] through the deprotonation reaction of the corresponding aminophosphine with nBuLi. X-ray diffraction analyses indicated the presence of Li-P bonds (2.684 and 3.004 Å). In addition, the P-N bond length (1.672(2) Å) was relatively smaller than that of a single bond (mean value of 1.70).