New and straightforward synthetic paths for the syntheses of [RNPNR]- anions (R = t-Bu (1) or CPh3 (6)) in the form of their tmeda- or thf-coordinated lithium salts are described. The attempts to isolate the sodium analogue [(Ph3CNPNCPh3)Na·(thf)x] (8) remained unsuccessful probably due to its high reactivity although its formation in the reaction of the parent cis-[(Ph3CNP)2(Ph3CNH)2] (5) with 2 eq. of sodium naphthalenide was corroborated by NMR spectroscopy. Importantly, when an excess of sodium naphthalenide was used in the reaction with 5, [(Ph3C)Na(thf)3] (9) was obtained along with a complex mixture of other by-products indicating the cleavage of the C-N bond in the starting material. Furthermore, the synthesis and the structural characterization of the [P(Nt-Bu)3]3- trianion as its trilithium salt [P(Nt-Bu)3Li3]2 (10) has been successfully achieved.