The
novel thioether-dithiolate-bridged diiron complex [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt)FeCp*] (1, Cp*
= η5-C5Me5; tpdt = S(CH2CH2S−)2) has been
prepared by the reaction of [Cp*FeCl]2 with Li2(tpdt) in THF. Given the thermodynamic instability of 1, a one-electron oxidation was performed with Fc·PF6 (Fc = ferrocene) affording 1[PF
6
]. Treatment of 1[PF
6
] with CO or
t
BuNC
in CH2Cl2 gave complexes [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt){Cp*Fe(η1-CO)}][PF6] (2[PF
6
]) and [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt){Cp*Fe(η1-
t
BuNC)}][PF6] (3[PF
6
]). In addition, complex 1[PF
6
] can be further oxidized into [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt)FeCp*][PF6]2 (1[PF
6
]
2
) by Fc·PF6 in THF, while in the presence
of MeCN resulting in the formation of complex [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt){Cp*Fe(η1-MeCN)}][PF6]2 (4[PF
6
]
2
). When the
solution of complex 1 in THF was warmed to room temperature,
thioether-dithiolate-bridged trinuclear iron complex [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt)Fe(μ-2κ
2
SS:3κ
3
SSS′-tpdt)FeCp*] (5), which can be oxidized
into complex [Cp*Fe(μ-1κ
3
SSS′:2κ
2
SS-tpdt)Fe(μ-2κ
2
SS:3κ
3
SSS′-tpdt)FeCp*][PF6]2 (5[PF
6
]
2
) with Fc·PF6, was
obtained accompanied by byproduct Cp*2Fe. 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(μ-1κ
3
SSS′:2κ
2
SS-tpdt)FeCl2] (7) can be prepared by the reaction of complex 6 with anhydrous FeCl2 in CH2Cl2. Complex 5[PF
6
]
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.
