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Indexed by:Journal Papers

Date of Publication:2015-05-11

Journal:ORGANOMETALLICS

Included Journals:SCIE、EI、Scopus

Volume:34

Issue:9

Page Number:1661-1667

ISSN No.:0276-7333

Abstract:The novel thioether-dithiolate-bridged diiron complex [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt)FeCp ] (1, Cp = eta(5)-C5Me5; tpdt = S(CH2CH2S-)(2)) has been prepared by the reaction of [Cp FeCl](2) with Li-2(tpdt) in THF. Given the thermodynamic instability of 1, a one-electron oxidation was performed with Fc PF6 (Fc = ferrocene) affording 1[PF6]. Treatment of 1[PF6] with CO or (BuNC)-Bu-t in CH2Cl2 gave complexes [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt){Cp Fe(eta(1)-CO)}][PF6] (2[PF6]) and [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt){Cp Fe(eta(1)-(BuNC)-Bu-t)}][PF6] (3[PF6]). In addition, complex 1[PF6] can be further oxidized into [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt)FeCp ][PF6](2) (1[PF6](2)) by Fc PF6 in THF, while in the presence of MeCN resulting in the formation of complex [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt){Cp Fe(eta(1)-MeCN)}][PF6](2) (4[PF6](2)). When the solution of complex 1 in THF was warmed to room temperature, thioether-dithiolate-bridged trinuclear iron complex [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt)Fe(mu-2(k)(2)SS:3(k)(3)SSS'-tpdt)FeCp ] (5), which can be oxidized into complex [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt)Fe(mu-2(k)(2)SS:3(k)(3)SSS'-tpdt)FeCp ][PF6](2) (5[PF6](2)) with Fc PF6, was obtained accompanied by byproduct Cp Fe-2. Complex 5 is sensitive to air and upon exposure to air in THF gave monoiron complex [Cp Fe(tpdt)] (6) in moderate yield. Complex 6 is a good metallothiolato precursor for synthesis of homo- and heterobimetallic or trimetallic complexes. The binuclear complex [Cp Fe(mu-1(k)(3)SSS':2(k)(2)SS-tpdt)FeCl2] (7) can be prepared by the reaction of complex 6 with anhydrous FeCl2 in CH2Cl2. Complex 5[PF6](2) can also be obtained by the reaction of complex 6 with FeCl2 or complex 7 in the presence of NH4 PF6. These complexes have been spectroscopically and crystallographically characterized.