Crystal and molecular structures of trans-[PdCl₂(SMePh)₂] ·C₆H₆, trans-[Pd₂Cl₂(μ-SPh)₂(SPh₂)₂], and trans-[Pd₂Cl₂(μ-SPh)₂(PPh₃)₂] · 4CH₂Cl₂

Article type: Research Article

Authors: Oilunkaniemi, Raija | Laitinen, Risto S. | Ahlgrén, Markku

Affiliations: Department of Chemistry, PO Box 3000, FI-90014 University of Oulu, Finland | Department of Chemistry, University of Joensuu, P.O. Box 111, FI-80101 Joensuu, Finland

Note: [] Corresponding author. E-mail: [email protected]

Abstract: 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.

Keywords: Thioether, Thiolato, Palladium complex, Crystal structure

DOI: 10.1080/10241220601087093

Journal: Main Group Chemistry, vol. 5, no. 2, pp. 125-136, 2006