Synthesis and Reactions of Novel Triply Thiolate-Bridged Diiron Complexes [Cp*Fe(μ₂-SR)₃FeCp*] (Cp* = η⁵-C₅Me₅; R = Et, Ph)

The novel thiolate-bridged diiron complexes [Cp*Fe(μ 2 -SR) 3 FeCp*] ( 1, R = Et; 2, R = Ph) have been obtained by the reaction of [Cp*FeCl] 2 with LiSEt or LiSPh in THF. Treatment of 1 with CO or CN t Bu in THF gives complex [Cp*FeSEt(μ 2 -SEt) 2 FeCp*CO] ( 3 ) or [Cp*FeSEt(μ 2 -SEt) 2 FeCp*CN t Bu] ( 4 ), while reaction of 1 with CN t Bu in CH 2 Cl 2 results in the formation of complex [Cl 2 Fe(μ 2 -SEt) 2 FeCp*CN t Bu] ( 5 ). These five complexes have been spectroscopically and crystallographically characterized. In addition, the formation of 5 indicates that this class of clusters might serve as carbon−halogen bond activation reagents (catalysts), and carbon−halogen bond cleavage reaction of 4 is also described.