B–H bond iodination of polyhedral dimolybdaborane and dimolybdathiaborane clusters

• Iodo substituted molybdaboranes and molybdathiaboranes have been synthesized.
• Iodination of metallaborane, metallaheteroborane achieved using LiBH4.thf and NaI.
• All the compounds were characterized by IR, 1H, 11B NMR and X-ray crystallography.

Reaction of [Cp∗MoCl4] (Cp∗ = η5-C5Me5) with excess of [LiBH4·thf] followed by pyrolysis with NaI yielded B–I inserted [(Cp∗Mo)2B5H9−nIn], 1–3 (1: n = 1; 2: n = 2; 3: n = 3). In parallel to the formation of 1–3, the reaction also produced known [(Cp∗Mo)2B5H9] and [(Cp∗Mo)2(μ-I)4] in good yields. Under the similar reaction conditions, dimolybdathiaborane [(Cp∗Mo)2B4H4S2] yielded iodine substituted dimolybdathiaboranes, [(Cp∗Mo)2B4S2H4−nIn], 4 and 5 (4: n = 2; 5: n = 3) in good yields. All the new compounds have been characterized in solution by IR, 1H and 11B NMR as simple substituted derivatives of [(Cp∗Mo)2B5H9] and [(Cp∗Mo)2B4H4S2]. The solid state structures were established unambiguously by crystallographic analysis of compounds 1–5.

Iodine substituted dimolybdaboranes [(Cp∗Mo)2B5H9−nIn] (n = 1, 2 or 3) and dimolybdathiaboranes [(Cp∗Mo)2B4H4−nS2In] (n = 2 or 3) have been synthesized and structurally characterized (see picture).Figure optionsDownload as PowerPoint slide