A combination of multinuclei NMR, UV-vis spectroscopy, and single crystal X-ray diffraction was used to characterize a new series of tripalladium ditropylium sandwich complexes [Pd(3)Tr(2)(E)(3)][BF(4)](2) (E = PPh(3), AsPh(3), and SbPh(3) and PEt(3)). Ligand substitution leads to a systematic shift of the (1)H and (13)C NMR tropylium resonances and is correlated with the electron donating properties of the substituent group. Replacement of the ligand increases the palladium-pnictogen bond length in the order P < As < Sb; however, this only slightly alters the internal Pd-Pd bond lengths, supporting the hypothesis that there are only weak Pd-Pd bonding interactions.
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