Synthesis and Characterization of Pyrrolthiosemicarbazone Complexes of Palladium(II). Crystal Structures of [{Pd[C4H4NC(H)=NNC(S)NHMe](Cl)}2{μ‐Ph2P(CH2)3PPh2}] and [Pd{C4H4NC(H)=NNC(S)NHMe}{Ph2P(CH2)2PPh2‐P, P}](Cl)

Reaction of the thiosemicarbazone ligands C4H4NC(H)=NN(H)C(S)NHR (R = Me, a; Et, b) with Li2[PdCl4] gave the dinuclear complexes [Pd{C4H4NC(H)=NNC(S)NHR}(μ-Cl)]2 (R = Me, 1a; Et, 1b) with a central Pd2Cl2 core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C4H4C(H)=NNC(S)NHR}(Cl)(PPh3)] (R = Me, 2a; Et, 2b), whereas reaction of 1a and 1b with tertiary diphosphines gave mono- and dinuclear compounds, as appropriate, with the corresponding diphosphine acting as a monodentate (6b), chelating (3a) and bridging ligand (4a, 5a, 4b, 5b). Treatment of 1a and 1b with (Ph2PCH2CH2PPh2)W(CO)5 gave the new heterobimetallic complexes 7a and 7b. The crystal structures of complexes 3a and 4a are described.