Abstract: | In the coordination chemistry of palladium, dimers bridged via halides are a common motif. Higher oligomers, however, are still rare. We report the structure of an alternating eight‐membered Pd4Br4]4? ring framed by cycloheptatrienide ligands, which was obtained by cocrystallization of dimers and tetramers of the complex salt bromido{η3‐3‐(2,6‐diisopropylphenyl)imidazolium‐1‐yl]cycloheptatrienido}palladium(II) tetrafluoroborate, namely bisdi‐μ‐bromido‐bis({η3‐3‐(2,6‐diisopropylphenyl)imidazolium‐1‐yl]cycloheptatrienido}palladium(II))] cyclo‐tetra‐μ‐bromido‐tetrakis({η3‐3‐(2,6‐diisopropylphenyl)imidazolium‐1‐yl]cycloheptatrienido}palladium(II)) octakis(tetrafluoroborate) dichloromethane octasolvate, Pd4Br4(C22H26N2)4]Pd2Br2(C22H26N2)2]2(BF4)8·8CH2Cl2. These dimers and tetramers form a highly dynamic equilibrium in solution which was studied by low‐temperature NMR spectroscopy. In the light of the presented results, tetrameric PdII species can be assumed to co‐exist as a second species in many cases where by current knowledge only a dimeric compound would be expected. |