Reaction between [RhCl(PPh3)3] and the [nido-6-NB9H11]− anion in CH2Cl2 yields orange eleven-vertex [8,8-(PPh3)2-nido-8,7-RhNB9H11] (1). Reaction of the [nido-6-CB9H12]− anion with [cis-PtCl2(PMe2Ph)2] in methanol affords yellow eleven-vertex [9-(OMe)-8,8-(PMe2Ph)2-nido-8,7-PtCB9H10] (2), which is also formed from the reaction of MeOH with [8,8-(PPh3)2-nido-8,7-PtCB9H10] (3). Both compounds have been characterised by single-crystal X-ray diffraction analysis and examined by NMR spectroscopy and have structures based on eleven-vertex nido-type geometries, with the metal centre and the heteroatoms in the adjacent (8)- and (7)-positions on the pentagonal open face. The metal-to-heteroborane bonding sphere of 1 is fluxional, with a ΔG‡ value of 48.4 kJ mol−1. DFT calculations on the model compounds [8,8-(PH3)2-nido-8,7-RhNB9H11] (1a) and [8,8-(PH3)2-nido-8,7-RhSB9H10] (4a) have been carried out to define the fluxional process and the intermediates involved.
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