Around 30 years ago, Razuvaev and co-workers [J. Organomet. Chem. 1980, 199, 205] reported a unique organometallic cluster (II) containing a metallocycle-based Ge 3 Bi 2 Pt core with the first manifestation of the Bi−Pt bonding. This multimetallic cluster was prepared by introducing the Pt(PPh 3 ) 2 moiety into the structure of a [(C 6 F 5 ) 6 Ge 3 Bi 2 ] complex (I). We, in turn, quantum chemically investigated fundamental aspects of the structure, stability, bonding, and reactivity of the model heteroelemental (H 2 E) 3 Bi 2 complexes and their ML 2 (L = PH 3 )-functionalized derivatives along E = C, Si, Ge, Sn, Pb and M = Ni, Pd, Pt families. The current work aims to assist the further development of synthetical approaches toward these classes of compounds and to afford new insights into the main group element (E, Bi)−transition metal (M) bonding. Our electronic structure calculations were based on relativistic density functional theory in combination with natural bond orbital and electron localization function analyses, and a quantitative energy decomposition analysis. They allowed identification of molecules, dubbed 1,3dibismuthabicyclo[1.1.1]carbenoidanes, that are composed of two Bi(0) atoms and three carbenoid H 2 E: units. Functionalization of the (H 2 E) 3 Bi 2 complexes with ML 2 moieties did not represent an oxidative addition, but rather the carbenoid-like insertion of ML 2 into the E−Bi bond of a bicyclo[1.1.1]pentane motif which is characteristic of the (H 2 E) 3 Bi 2 structures. Such an insertion resulted in the formation of the covalently bonded (H 2 E) 3 Bi 2 [ML 2 ] compounds. Our computational analyses suggest that the compounds, comprising silicon atoms as E, possess the best stability and may be the most viable targets for synthesis.
