Abstract
The metalation of triisopropylsilyl- and tri(tert-butyl)silylphosphane with alkaline earth metal bis[bis(trimethylsilyl)amides] yields the corresponding phosphanides. Depending on the stoichiometry, the dimeric and heteroleptic or homoleptic derivatives [(Me3Si)2N]nM2[μ-P(H)SiR3]4-n with n = 0, 1, and 2 are isolated and can be regarded as steps on the way to M2nP2m cage compounds in which the ratio n/m can vary between 1/2 [metal bis(phosphanides)] and 1/1 (metal phosphandiides). The metalation of triisopropylsilyl- and tri(tert-butyl)silyl-phosphane with dibutylmagnesium gives Mg2nP2m cages with n/m = 1/1, 2/3, and 4/5. The heavier alkaline earth metals form M2nP2m cages with n/m = 1/2 and 3/4 (M = Ca, Sr, Ba) in which the ratio n/m = 1/2 represents the homoleptic dimeric alkaline earth metal bis(phosphanide). All these cages can be derived from a M2P2 cycle which appears dimeric (M4P4 heterocubane) or trimeric (hexagonal M6P6 prism) in which two opposite planes can be capped by alkaline earth metal bis(phosphanide) molecules.
Published Version
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