A Cyclometallated (Azobenzene)palladium(II) Complex of 1,4,7-Trithiacyclononane: Synthesis and Reactivity with Thioether-Dithiolate Metalloligands, Single-Crystal X-ray Diffraction Analyses and Electrochemical Studies

作者：Shin Richard Y C; Goh Chun Lian; Goh Lai Yoong^*; Webster Richard D; Li Yongxin

来源：European Journal of Inorganic Chemistry, 2009, 2009(15): 2282-2293.

DOI：10.1002/ejic.200900049

• Palladium
• Heterometallic complexes
• S ligands
• Ruthenium
• Crown compounds

The treatment of [{Pd(C(6)H(4)N=NC(6)H(5))(mu-Cl)}(2)] (5) with AgPF(6)/NH(4)PF(6) in acetone, followed by the addition of two molar equivalents of 1,4,7-trithiacyclononane (9S3), gives the deep red complex [Pd(C(6)H(4)N=NC(6)H(5))(9S3)][PF(6)] (6A) in high yield, whereas the direct reaction of 5 with two molar equivalents of 9S3 gives [Pd(C(6)H(4)N=NC(6)H(5))(9S3)][Pd(C(6)H(4)N=NC(6)H(5))Cl(2)] (6B) in quantitative yield based on 5. The subsequent reaction of 5 and 6A with the metalloligand [(HMB)Ru(II){eta(3)-tpdt}] [3; HMB = eta(6)-C(6)Me(6), tpdt = S(CH(2)CH(2)S(-))(2)] results in displacement of the chloride and 9S3 ligands, respectively, to give the Ru-Pd heterobimetallic complex [{(HMB)Ru(II)(mu-eta(2):eta(3)-tpdt)}{Pd(C(6)H(4)N=NC(6)H(5))}][PF(6)] (7) in 85% yield. Similar reactions with the Cp* analogue of 3, namely [(Cp*)Ru(III){eta(3)-tpdt}] (4), give the trinuclear complex [{Cp*Ru(III)(mu-eta(2):eta(3)-tpdt)}(2)Pd](PF(6))(2) (8), in which all the ligands on palladium have been displaced, in a yield of around 80%. X-ray diffraction analyses of 6A, 6B and its solvates (6B center dot H(2)O and 6B center dot CHCl(3)) have shown that short atom-atom interactions between the cation and the counterion and lattice solvent molecules have a significant effect on the bond parameters of the molecules, and (1)H NMR spectroscopy indicates that these interactions persist even in solution. The single-crystal X-ray structure of 7 has also been determined. Cyclic voltammetry experiments have been performed on 6A, 6B and 7 in CH(2)Cl(2) and CH(3)CN at GC and Pt electrodes.

• 出版日期2009-5
• 单位南阳理工学院