16-Vertex oblato - hypho -titanaborane [(Cp*Ti) 2 B 14 H 18 ].

Although Lipscomb predicted in 1977 that supra-icosahedral boron clusters would be viable, their synthesis has been impeded by the unavailability of appropriate synthetic methodologies. Herein, we report the first examples of the open 16-vertex oblato - hypho -titanaborane clusters [(Cp*Ti) 2 B 14 H 17 R] (1: R = H; 2: R = Me) having a non-Wadean 19-skeletal-electron-pair count. Interestingly, these clusters show a six-membered [Ti 2 B 4 ] open face, which could lead to closo -19-vertex clusters.