Synthesis and cyclic voltammetry of trinuclear [Pd 3(μ 3-E) 2(dpae) 3] 2+ clusters; E=S, Se or Te; dpae=1,2-bis(diphenylarsino)ethane and X-ray structure of [Pd 3(μ 3-S) 2(dpae) 3][BPh 4] 2

• Published in: Polyhedron 1999-05, Vol.18 (13), p.1811-1814
• Main Authors: Matsumoto, Keiji, Takahashi, Kazumitsu, Hada, Satomi, Nakao, Yasuo
• Format: Article
• Language: English
• Subjects: Chalcogenido ions, 1,2-Bis(diphenylarsino)ethane; Palladium; Trinuclear cluster; X-ray structure
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(99)00059-5

The trinuclear clusters [Pd 3(μ 3-E) 2(dpae) 3][BPh 4] 2 (E=S ( 1), Se ( 2) or Te ( 3); dpae=1,2-bis(diphenylarsino)ethane) were synthesized and the crystal structure of [Pd 3(μ 3-S) 2(dpae) 3][BPh 4] 2 1 was determined by X-ray diffraction methods. The structure of [Pd 3(μ 3-S) 2(dpae) 3] 2+ comprises three square planar PdS 2As 2 coordination planes sharing two μ 3-S 2− ions. In the central trigonal bipyramidal Pd 3S 2 core the interatomic distances are Pd–S 2.337(mean) and S⋯S 3.083(7) Å; there are two shorter Pd⋯Pd distances of 3.008(3) and 2.998(2) Å and one longer Pd⋯Pd distance of 3.117(3) Å. The reduction process of 1, 2 and 3 has been studied by cyclic voltammetry. The clusters 2 and 3 are reversibly reduced and oxidized at the scan rate of 500 mV s −1 and 100 mV s −1, respectively at 255 K. The cluster 1 is not reduced reversibly at a scan rate of 500 mV s −1 at 255 K. The ease of reduction and the extent of reversibility are in the order Te>Se>S for the [Pd 3(μ 3-E) 2(dpae) 3][BPh 4] 2 clusters.