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(μ2-SR)3FeCp*] (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 CNtBu in THF gives complex [Cp*FeSEt(μ2-SEt)2FeCp*CO] (3) or [Cp*FeSEt(μ2-SEt)2FeCp*CNtBu] (4), while reaction of 1 with CNtBu in CH2Cl2 results in the formation of complex [Cl2Fe(μ2-SEt)2FeCp*CNtBu] (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.本研究通过将[Cp*FeCl]₂与乙硫醇锂（LiSEt）或苯硫酚锂（LiSPh）在四氢呋喃（THF）中反应，成功制备了新型硫醇盐桥联二铁配合物[Cp*Fe(μ₂-SR)₃FeCp*]（1，R=Et；2，R=Ph）。将配合物1分别与一氧化碳（CO）或叔丁基异腈（CNtBu）在四氢呋喃中反应，分别得到配合物[Cp*FeSEt(μ₂-SEt)₂FeCp*CO]（3）与[Cp*FeSEt(μ₂-SEt)₂FeCp*CNtBu]（4）；而当配合物1与叔丁基异腈在二氯甲烷（CH₂Cl₂）中反应时，则生成配合物[Cl₂Fe(μ₂-SEt)₂FeCp*CNtBu]（5）。上述五种配合物均通过光谱学与晶体学方法完成了表征。此外，配合物5的生成表明该类团簇可作为碳-卤键活化试剂（催化剂），本研究同时报道了配合物4的碳-卤键裂解反应。