Ligand-Free Deltahedral Clusters of Silicon in Solution: Synthesis, Structure, and Electrochemistry of Si92-

Abstract

Deltahedral nine-atom clusters of silicon, Si(9)(2-), were synthesized by mild oxidation of a liquid ammonia solution of K(12)Si(17) with Ph(3)GeCl in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) or 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane). The clusters were structurally characterized in [K(18-crown-6)](2)Si(9).C(5)H(5)N (yellow; orthorhombic, Pnma; a = 14.013(1), b = 18.108 (1), c = 18.320 (1) A; Z = 4) crystallized from a pyridine solution of the product of the aforementioned reaction in liquid ammonia. Si(9)(2-) is the first unequivocally characterized nine-atom cluster of group 14 with a charge of 2-. In addition to pyridine, the product from the reaction in liquid ammonia is also soluble in DMF, and the Si(9)(2-) clusters were characterized by mass spectrometry in such a solution. The more reduced clusters Si(9)(3-) have also been crystallized from pyridine solution. Cyclic voltammetry in both pyridine and DMF solutions clearly shows the Si(9)(2-)/Si(9)(3-) redox couple as one-electron reversible process. The structural similarities and differences between Si(9)(3-) and Si(9)(2-) are discussed herein.