Abstract
A new o‐phenylene‐bridged diseleno‐dithioether ligand tethered with an extremely bulky substituent, 2,4,6‐tris[bis(trimethylsilyl)‐methyl]phenyl (Tbt) group, at both terminal selenium atoms, [TbtSe(o‐phenylene)S]~2~(o‐phenylene) (3), was synthesized by taking advantage of the reaction of TbtSeSeTbt (4) with 1,2‐diiodobenzene using Cu~2~O in 2,4,6‐trimethylpyridine followed by the successive coupling reaction of the resulting bulky o‐iodophenylselenide (5) with 1,2‐benzenedithiol. Complexation of 3 with Na~2~PdCl~4~ gave the corresponding dichloropalladium(II) complex, [PdCl~2~(3)] (6). The X‐ray structural analysis of 6 indicated that the central palladium metal is in a distorted octahedral environment, where the two inner sulfur atoms of 3 and the two chlorine atoms form a square planar arrangement around the palladium metal and the two terminal selenium atoms of 3 weakly coordinate to the palladium center at the axial positions. The AIM calculations also indicated the existence of the interaction between palladium and selenium atoms in the crystalline state. On the other hand, the ^77^Se NMR spectrum suggests that there are no or very weak interactions between the palladium and selenium atoms of 3 in solution. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:549–556, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20339