Pnictogen–Silicon Analogues of Benzene

Since the discovery of the first “inorganic benzene” (borazine, B3N3H6), the synthesis of other noncarbon derivatives is an ongoing challenge in Inorganic Chemistry. Here we report on the synthesis of the first pnictogen–silicon congeners of benzene, the triarsa- and the triphospha-trisilabenzene [(PhC­(NtBu)2)3Si3E3] (E = P (1a), As (1b)) by a simple metathesis reaction. These compounds are formed by the reaction of [Cp″2Zr­(η1:1-E4)] (E = P, As; Cp″ = C5H3tBu2) with [PhC­(NtBu)2SiCl] in toluene at room temperature along with the silicon pnictogen congeners of the cyclobutadiene, [(PhC­(NtBu)2)2Si2E2] (E = P (2a), As (2b)), which is unprecedented for the arsenic system 2b. All compounds were comprehensively characterized, and density functional theory calculations were performed to verify the stability and the aromatic character of the triarsa- and the triphospha-trisilabenzene.