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.

Graphical abstractIodine 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 full-size imageDownload as PowerPoint slide