AbstractThe first metal‐carbon bond β‐form paddlewheel complexes containing a Pd24+core, [Pd(η2‐dithio)]2(μ‐dppa)( μ‐SCNMe2) (dithio = S2P(OEt)2,2; S2COEt,3; S2CNC4H8,4), were prepared by the reactions of the α‐form paddlewheel‐type Pd2+4dipalladium complex [Pd2(μ‐Hdppa)2(μ‐SCNMe2)2][Cl]2,1with various dithio‐ligands, [NH4][S2P(OEt)2], [K][S2COEt] and [NH4][S2CNC4H8], in methanol at ambient temperature (Hdppa = bis(diphenylphosphino)amine). Electronic spectra and two X‐ray structures of the Pd2+4