Fusing Triphenylbismuth and PnPh₃ (Pn = P-Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes

The first series of 9-bisma-10-pnictatriptycenes Bi(C6H4)(3)Pn (2-Pn, Pn = P-Bi; see graphic) has been synthesized in a two-step procedure via suitable tris(2-bromophenyl)pnictanes 1-Pn and characterized in solution as well as in the solid state. DFT calculations suggest preferential interactions between 2-Pn and soft Lewis acids via the lighter pnictogen donor atom. Experimental studies demonstrate that even the weakest Lewis base in the series of 2-Pn, namely the dibismatriptycene 2-Bi, interacts with Lewis acidic [BiMe2(SbF6)] in solution. Analytical techniques include (VT-)NMR spectroscopy, DOSY NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, and DFT calculations.