Mechanochemical synthesis and structural analysis of trivalent lanthanide and uranium diphenylphosphinodiboranates

Phosphinodiboranates (H₃BPR₂BH₃^-) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H₃BP^tBu₂BH₃) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et₂O and THF. Here we report how this reactivity appears to be further attenuated in solution when the ^tBu groups attached to phosphorus are exchanged for R = Ph or H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H₃BPPh₂BH₃). Grinding three equivalents of K(H₃BPPh₂BH₃) with UI₃(THF)₄ or LnI₃ (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H₃BPPh₂BH₃)₃ (1), Ce(H₃BPPh₂BH₃)₃ (2), Pr(H₃BPPh₂BH₃)₃ (3), and Nd(H₃BPPh₂BH₃)₃ (4) to be prepared and subsequently crystallized in good yields (50-80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas ¹H and ¹¹B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H₃BPPh₂BH₃)₃(THF)₃ (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H₃BPPh₂BH₃^- ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H₃BPPh₂BH₃), attempting the same mechanochemical reactions with Na(H₃BPH₂BH₃) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H₃BPH₂BH₃)I₂(THF)₃ (5) was isolated in poor yields. Despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.