Coordination of Ligands That Contain Thiocarbonyl, Carbonyl, or Thiolate Functionalities to Complex Fragments of Palladium in Various Oxidation States

Two phosphine ligands of [Pd(PPh 3 ) 4 ] were substituted by π (CS) coordination of 4‐bromodithiobenzoic acid methyl ester resulting in complex 1 . The same ester, after alkylation, afforded the dicationic complex bis( μ ‐methanethiolato)tetrakis(triphenylphosphine)dipalladium(2+) bis(tetrafluoroborate) ( 2 ) from the same palladium source. A related thiolato‐bridged complex, bis( μ ‐methanethiolato)bis(1‐methylpyridin‐2(1 H )‐ylidene)bis(triphenylphosphine)dipalladium(2+) bis(tetrafluoroborate) ( 4 ) and the trinuclear cluster tris( μ ‐methanethiolato)tris(triphenylphosphine)tripalladium(+)(3 PdPd ) ( 5 ) resulted from treatment of a known cationic pyridinylidene complex with MeSLi. The double oxidative substitution reaction of [Pd(PPh 3 ) 4 ] with 1,5‐dichloro‐9,10‐anthraquinone afforded trans ‐dichloro[ μ ‐(9,10‐dihydro‐9,10‐dioxoanthracene‐1,5‐diyl)]tetrakis(triphenylphosphine)dipalladium ( 6 ). Some of these complexes could be fully characterized by 1 H‐, 13 C‐, and 31 P‐NMR spectroscopy, mass spectrometry, and elemental analysis. The crystal and molecular structures of all of them, and of trans ‐bis(1,3‐dihydro‐1,3‐dimethyl‐2 H ‐imidazol‐2‐ylidene)diiodopalladium ( 3 ), were determined by single‐crystal X‐ray diffraction.