The reaction of neat methylphenylsulfide with PdCl2 affords trans-(PdCl2(SMePh)2). Upon recrystallization from dilute benzene/diethyl ether solution, crystals of trans, syn-(PdCl2(SMePh)2) · C6H6 (1 · C6H6) were isolated. (PdCl2(NCPh)2) in diphenylsulfide affords crystals of trans-(PdCl2(SPh2)2) and trans-(Pd2Cl2(μ-SPh)2(SPh2)2) (2). The latter species is a novel complex containing both thioether and thiolato ligands. A small amount of crystals of (Pd2Cl2(μ-SPh)2(PPh3)2) · 4CH2Cl2(3 · 4CH2Cl2) were isolated upon prolonged reflux a mixture of (PdCl2(PPh3)2) and Ph2S in CH2Cl2. Each Pd center shows a slightly distorted square-planar coordination. The Pd-S bond lengths involving Ph2S are 2.319(1) – 2.320(1)Å and 2.341(2)Å in 1 · C6H6 and 2, respectively and those involving bridging phenyl thiolato ligands are 2.301(2) – 2.312(2)Aring; and 2.296(1) – 2.375(1)Aring; in 2 and 3 · 4CH2Cl2, respectively. The lengths of the Pd–S bonds in 1 – 3 expectedly show a increasing trend consistent with the increasing trans influence Cl < S < P of the ligands trans to the thiolato or thioether ligands. All lattices are composed of discrete complexes that are linked together into three-dimensional networks by Cl···S and H···Cl close contacts.
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