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Indexed by:期刊论文

Date of Publication:2017-06-07

Journal:DALTON TRANSACTIONS

Included Journals:SCIE、EI、PubMed

Volume:46

Issue:21

Page Number:7030-7038

ISSN No.:1477-9226

Abstract: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.