The N-benzhydrylamido-1,1-diphenylphosphine-borane ligand [Ph 2P(BH3)NH(CHPh2)] (1-H) has been prepared via the reaction of an equimolar ratio of the phosphine amine [Ph 2PNH(CHPh2)] and the borane adduct [BH3· SMe2] at an ambient temperature. The reaction of 1-H with ((trimethylsilyl)methyl)lithium (neosilyllithium), [LiCH2SiMe 3], afforded a three-membered lithium amidophosphine-borane complex with the composition ([η2-Ph2CHNP(BH 3)Ph2)Li(THF)2] (2). Analogous reactions with sodium and potassium bis(trimethylsilyl)amides at ambient temperature yielded the respective alkali-metal amidophosphine-borane complexes [{(Ph 2CHNP(BH3)Ph2)Na(THF)2} 2] (3) and [{(Ph2CHNP(BH3)Ph 2)K(THF)2}2] (4), with the loss of hexamethyldisilazane, [(Me3Si)2NH]. The corresponding heavier alkaline-earth-metal complexes [M(THF)2{Ph 2P(BH3)N(CHPh2)}2] (M = Ca (5), Sr (6), Ba (7)) can be obtained via the reaction of [M{N(SiMe3) 2}2(THF)n] (M = Ca, Sr, Ba) and 1-H. The metal complexes 5-7 can also be prepared via a salt metathesis route, where the alkali-metal salts 3 and 4 were reacted with the respective metal diiodides in THF at ambient temperature. The molecular structures of 1-H and 2-7 have been established by X-ray diffraction analyses, and from the solid-state structures of 3-7, it was confirmed that, in all of the compounds, the metal ions are chelated through the nitrogen atom and the hydrogen atoms of the borane group of ligand 1-H. © 2013 American Chemical Society.