A Reversible NO-Triggered Multiple Metallaborane Cluster Fusion by Ligand Expulsion/Addition from (PMe2Ph)4Pt2B10H10 to Afford (PMe2Ph)8Pt8B40H40 and (PMe2Ph)5Pt4B20H20.

The dimetallic boron hydride cluster, (PMe2Ph)4Pt2B10H10 (1-Pt2), is known to reversibly sequester small molecules (e.g., O2, CO, and SO2) across its Pt-Pt cluster vector. Here, we report the very different effect of the addition of nitric oxide (NO) to solutions of (1-Pt2) that prompts the elimination of some of its phosphine ligands and the autofusion of the resultant {(PMe2Ph)xPt2B10H10} units to afford the metallaborane conglomerates (PMe2Ph)8Pt8B40H40 (2-Pt8, 38%) and (PMe2Ph)5Pt4B20H20 (3-Pt4, 34%). Single-crystal X-ray studies of these multicluster assemblies reveal the links between the clusters to be a combination of both Pt-Pt bonds and Pt-μH-B 2-electron, 3-center bonds in (2-Pt8) and Pt-μH-B 2-electron, 3-center bonds in (3-Pt4). For compound (2-Pt8), the cluster assemblage can be effectively reversed by the addition of ethyl isonitrile (EtNC) to afford (EtNC)3(PMe2Ph)2Pt2B10H10 4 in quantitative yield. The compounds were characterized by mass spectrometry, multielement NMR spectroscopy, and single-crystal X-ray diffraction studies.