Cyclic Hydrocarbon Frameworks Containing Two Bismuth Atoms: Towards 9,10-Dibismaanthracene

When bismuth atoms are incorporated into cyclic organic systems, this commonly goes along with strained or distorted molecular geometries, which can be exploited to modulate the physical and chemical properties of these compounds. In six-membered heterocycles, bismuth atoms are often accompanied by oxygen, sulfur or nitrogen as a second hetero-element. In this work, we present the first examples of six-membered rings, in which two CH units are replaced by BiX moieties (X=Cl, Br, I), resulting in dihydro-anthracene analogs. Their behavior in chemically reversible reduction reactions is explored, aiming at the generation of dibisma-anthracene (bismanthrene). Heterometallic compounds (Bi/Fe, Bi/Mn) are introduced as potential bismanthrene surrogates, as supported by bismanthrene-transfer to selenium. Analytical techniques used to investigate the reported compounds include NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, and DFT calculations. The first examples of dinuclear bismuth heterocycles featuring the dihydro-dibismaanthrace structural motif are presented. These compounds involve bismuth halides, selenides, and heterobimetallic bismuth / transition-metal compounds with a versatile coordination chemistry. Synthetic access to the low-valent highly reactive dibismaanthracene (the so-called bismanthrene) has been probed and transition-metal-based bismanthrene surrogates are suggested.image