点击次数：

论文类型：期刊论文

发表时间：2017-06-07

发表刊物：DALTON TRANSACTIONS

收录刊物：SCIE、EI、PubMed

卷号：46

期号：21

页面范围：7030-7038

ISSN号：1477-9226

摘要：The thioether-dithiolate-bridged heterotrinuclear complexes [Cp* Fe(mu-1(K)(3)SSS':2(K)(2)SS-tpdt) M(mu-2(K)(2)SS:3(K)(3)SSS'-tpdt) FeCp*][PF6](2) (Cp* = eta(5)-C5Me5; tpdt = S(CH2CH2S)(2);2, M = Co; 3, M = Ni; 4, M = Pd) have been prepared by a reaction of [Cp*Fe(eta(3)-tpdt)] (1) with complexes CoCl2, NiCl2(PPh3)(2), and PdCl2(PPh3)(2), respectively. Similarly, treatment of complex 1 with CuCl(PPh3) or AgPF6 afforded two heterotrinuclear complexes, [Cp*Fe(mu-1(K)(3)SSS':2(K)(2)SS-tpdt) M(mu-2(K)(2)SS:3(K)(3)SSS'-tpdt) FeCp*][PF6] (5, M = Cu; 6, M = Ag), while reaction of 1 with the complex AuCl(PPh3) gave a heterobinuclear complex, [Cp* Fe(mu-1(K)(3)SSS':2(K)(1)S-tpdt) Au(PPh3)][PF6] (7). These complexes have been spectroscopically and crystallographically characterized. An X-ray diffraction analysis showed that complexes 2, 3, 5, and 6 feature a heterometal center binding four sulfur atoms of two tpdt ligands with a cis orientation. However, in the Pd-containing complex 4, two tpdt ligands are arranged in a trans configuration. The mu(eff) data and EPR results indicate that complexes 2, 4, 5, 6, and 7 are paramagnetic and only complex 3 is diamagnetic. Electrochemical experiments on these heteronuclear clusters were performed at room temperature. Discrepancy of the redox couples in the CV plots of these complexes indicates different one-electron transfer processes.