Unique Coordination of Two CC Double Bonds to an Electron-Deficient Lead Center

Reaction of bis(cyclopentenemethyl)diethylplumbane (2) with trityl cation leads to the formation of the plumbyl cation bis(cyclopentenemethyl)plumbylium (1), in which the positively charged lead atom interacts with the two CC double bonds of the cyclopentene ligands. The plumbyl cation 1 is characterized by NMR spectroscopy (δ(207Pb)=807 ppm, δ(13C(CC))= 136.1 ppm, 1J(Pb,CC)=14.4 Hz) and Xray crystallography. The structure of 1 reveals a distorted trigonal‐bipyramidal coordination sphere for the lead atom with a unique coordination of two CC double bonds in apical positions. According to quantum‐mechanical calculations (MP2/6‐311G(d,p) (C, H), SDD (Pb)//MP2/6‐31G(d), SDD (Pb)) this interaction stabilizes 1 by 28.3 kcal mol−1 relative to the tricoordinated plumbylium ion 10. An “atoms in molecules” (AIM) analysis indicates a π‐type interaction between the lead atom and the CC double bonds, reminiscent of that in the 2norbornyl cation. Surprisingly stable is the cationic bisalkenyl complex of trivalent lead (1), which is formed under non‐nucleophilic reaction conditions by reaction of plumbane 2 with a trityl cation.