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Abstract

Silafulleranes with endohedral Cl^– ions are a unique, scarcely explored class of structurally well-defined silicon clusters and host-guest complexes. Herein, we report regioselective derivatization reactions on the siladodecahedrane [nBu₄N][Cl@Si₂₀(SiCl₃)₁₂Cl₈] ([nBu₄N][1]), which has its cluster surface decorated with 12 SiCl₃ and 8 Cl substituents in perfect T_h symmetry. The room-temperature reaction of [nBu₄N][1] with excess iBu₂AlH in ortho-difluorobenzene (oDFB) furnishes perhydrogenated [nBu₄N][Cl@Si₂₀(SiH₃)₁₂H₈] ([nBu₄N][2]) in 50% yield; the non-pyrophoric [2]⁻ is the largest structurally authenticated (by X-ray diffraction) hydridosilane known to date. A simple switch from pure oDFB to an oDFB/Et₂O solvent mixture suppresses core hydrogenation and results in the formation of [nBu₄N][Cl@Si₂₀(SiH₃)₁₂Cl₈] ([nBu₄N][3]). In addition to the exhaustive Cl/H exchange at all 44 Si–Cl bonds of [1]⁻ and the regioselective 36-fold silyl group hydrogenation, we achieved the simultaneous introduction of Me substituents at all 8 SiCl vertices along with the conversion of all 12 SiCl₃ to SiH₃ groups by treating [nBu₄N][1] with Me₂AlH/Me₃Al in oDFB ([nBu₄N][Cl@Si₂₀(SiH₃)₁₂Me₈], [nBu₄N][4]; 73%). Quantum-chemical free-energy calculations find an S_N2-Si-type hydrogenation of the exohedral SiCl₃ moieties in [1]⁻ (trigonal-bipyramidal intermediate) slightly preferred over metathesis-like S_Ni-Si substitutions (four-membered transition state). Cage hydrogenation likely occurs via S_Ni-Si processes. The experimentally demonstrated influence of an Et₂O co-solvent, which drastically increases the respective reaction barriers, is attributed to the increased stability of the resulting iBu₂AlH-OEt₂ adduct and its higher steric bulk compared to free iBu₂AlH.