The reaction of the anti-B18H22 borane cluster with nickelocene produced several new metallaborane species, [Ni(THF)4(H2O)2][B18H20Ni(η5-C5H5)]2 (1a), [B18H20Ni(η5-C5H5)] (1b) and [N(CH3)4][B18H19(2-THF)Ni(η5-C5H5)] (2), in relatively high yields. These new complexes were fully characterized by multinuclear NMR (1H, 13C, 11B), IR and UV-Vis spectroscopy. Single-crystal X-ray diffraction analyses of complexes 1a and 2 confirmed their structures as 19-vertex conjuncto-metallaborane
clusters. The structures consist of ten-vertex nido-borane subunits edge-shared with eleven-vertex nido-cluster subunits. In compound 2, formed through the THF reflux of compound 1, a THF molecule was found to coordinate at the 2-position of the borane framework.
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