The First Metal‐Carbon Bond β‐Isomer Paddlewheel Pd 2 4+ Compounds

The first metal‐carbon bond β‐form paddlewheel complexes containing a Pd 2 4+ core, [Pd(η 2 ‐dithio)] 2 (μ‐dppa)( μ‐SCNMe 2 ) (dithio = S 2 P(OEt) 2 , 2 ; S 2 COEt, 3 ; S 2 CNC 4 H 8 , 4 ), were prepared by the reactions of the α‐form paddlewheel‐type Pd 2 +4 dipalladium complex [Pd 2 (μ‐Hdppa) 2 (μ‐SCNMe 2 ) 2 ][Cl] 2 , 1 with various dithio‐ligands, [NH 4 ][S 2 P(OEt) 2 ], [K][S 2 COEt] and [NH 4 ][S 2 CNC 4 H 8 ], in methanol at ambient temperature (Hdppa = bis(diphenylphosphino)amine). Electronic spectra and two X‐ray structures of the Pd 2 +4 species have been determined.