Liu Liang, Rauchfuss Thomas B, Woods Toby J
School of Chemical Sciences , University of Illinois , Urbana , Illinois 61801 , United States.
Inorg Chem. 2019 Jul 1;58(13):8271-8274. doi: 10.1021/acs.inorgchem.9b01231. Epub 2019 Jun 11.
Described is the preparation of the first iron carbide-sulfides. The cluster [FeC(CO)(SO)] ([2]), which is generated quantitatively from [FeC(CO)] ([1]), was O-methylated to give the sulfinite [2Me]. Demethoxylation of [2Me] with BF gave the face-capped octahedral cluster FeC(CO)(SO) (3). In solution, 3 spontaneously converted to the sulfide FeC(CO)(S) (4), an edge-fused double cluster with FeC and FeS subunits. Although 4 undergoes 1e reduction reversibly, 2e reduction (or base hydrolysis) of 4 gives closo-[FeC(CO)(S)] ([5]). The synthetic entries into the FeCS manifold may underpin the preparation of active-site analogues of the FeMoco and FeVco cofactors.
首次报道了碳化铁硫化物的制备。由[FeC(CO)]（[1]）定量生成的簇合物[FeC(CO)(SO)]（[2]）经O-甲基化得到亚磺酸盐[2Me]。用BF对[2Me]进行脱甲氧基化得到面盖帽八面体簇合物FeC(CO)(SO)（3）。在溶液中，3自发转化为硫化物FeC(CO)(S)（4），这是一种具有FeC和FeS亚基的边缘稠合双簇合物。尽管4可逆地进行1e还原，但4的2e还原（或碱水解）得到封闭型[FeC(CO)(S)]（[5]）。进入FeCS体系的合成方法可能为铁钼辅因子和铁钒辅因子活性位点类似物的制备提供基础。
