Treatment of P-4 with in situ generated [Na][SnPh3] leads to the formation of the sodium monophosphide [Na][P(SnPh3)(2)] and the Zintl salt [Na](3)[P-7]. The former was isolated in 46% yield as the crystalline salt [Na(benzo-15-crown-5)][P(SnPh3)(2)] and used to prepare the homoleptic phosphine P(SnPh3)(3), isolated in 67% yield, as well as the indium derivative (XL)(2)InP(SnPh3)(2) (XL = S(CH2)(2)NMe2), isolated in 84% yield, and the gold complex (Ph3P)AuP(SnPh3)(2). The compounds [Na(benzo-15-crown-5)][P(SnPh3)(2)], P(SnPh3)(3), (XL)(2)InP(SnPh3)(2), and (Ph3P)AuP(SnPh3)(2) were characterized using multinuclear NMR spectroscopy and X-ray crystallography. The bonding in (Ph3P)AuP(SnPh3)(2) was dissected using natural bond orbital (NBO) methods, in response to the observation from the X-ray crystal structure that the dative P -> Au bond is slightly shorter than the shared electron-pair P-Au bond. The bonding in (XL)(2)InP(SnPh3)(2) was also interrogated using P-31 and C-13 solid-state NMR and computational methods. Co-product [Na](3)[P-7] was isolated in 57% yield as the stannyl heptaphosphide P-7(SnPh3)(3), following salt metathesis with ClSnPh3. Additionally, we report that treatment of P-4 with sodium naphthalenide in dimethoxyethane at 22 degrees C is a convenient and selective method for the independent synthesis of Zintl ion [Na](3)[P-7]. The latter was isolated as the silylated heptaphosphide P-7(SiMe3)(3), in 67% yield, or as the stannyl heptaphosphide P-7(SnPh3)(3) in 65% yield by salt metathesis with ClSiMe3 or ClSnPh3, respectively.