School of Chemical Sciences , University of Illinois , Urbana , Illinois 61801 , United States.
Inorg Chem. 2019 Feb 18;58(4):2761-2769. doi: 10.1021/acs.inorgchem.8b03344. Epub 2019 Feb 6.
The chemistry of Fe(μ-SH)(CO)(PPh) (2) is described with attention to S-S coupling reactions. Produced by the reduction of Fe(μ-S)(CO)(PPh) (2), 2 is an analogue of Fe(μ-SH)(CO) (1), which exhibits well-behaved S-centered redox. Both 2 and the related 2 exist as isomers that differ with respect to the stereochemistry of the μ-SR ligands (R = H, Me). Compounds 2, 2, and 2 protonate to give rare examples of Fe-SH and Fe-S hydrides. Salts of [H2], [H2], and [H2] were characterized crystallographically. Complex 2 reduces O, HO, (PhCO), and PhN, giving 2. Related reactions involving 1 gave uncharacterizable polymers. The differing behaviors of 2 and 1 reflect stabilization of the ferrous intermediates by the PPh ligands. When independently generated by the reaction of 2 with 2,2,6,6-tetramethyl-1-piperidinyloxy, 2* quantitatively converts to 2 or, in the presence of CH, is trapped as the ethanedithiolate Fe(μ-SCH)(CO)(PPh). Evidence is presented that the Hieber-Gruber synthesis of 1 involves polysulfido intermediates [Fe(μ-S )(CO)] ( n > 1). Two relevant experiments are as follows: (i) protonation of [Fe(μ-S)(μ-S)CO)] gives 1 and 1, and (ii) oxidation of 1 by sulfur gives 1.
描述了 Fe(μ-SH)(CO)(PPh) (2) 的化学性质，并特别关注了 S-S 偶联反应。2 是 Fe(μ-S)(CO)(PPh) (2) 的还原产物，是 Fe(μ-SH)(CO) (1) 的类似物，具有良好的 S 中心氧化还原性质。2 和相关的 2 都以μ-SR 配体（R = H，Me）立体化学不同的异构体形式存在。化合物 2 和 2 质子化，得到了 Fe-SH 和 Fe-S 氢化物的罕见实例。[H2]、[H2]和[H2]的盐通过晶体学进行了表征。2 还原了 O、HO、(PhCO)和 PhN，得到了 2。涉及 1 的相关反应得到了无法表征的聚合物。2 和 1 的不同行为反映了 PPh 配体对亚铁中间体的稳定作用。当 2 与 2,2,6,6-四甲基-1-哌啶氧基独立反应时，2*定量转化为 2，或者在 CH 的存在下，作为乙二硫醇根 Fe(μ-SCH)(CO)(PPh)捕获。有证据表明，1 的 Hieber-Gruber 合成涉及多硫中间体[Fe(μ-S )(CO)] ( n > 1)。两个相关的实验如下：(i)质子化[Fe(μ-S)(μ-S)CO)]得到 1 和 1，(ii)氧化 1 得到 1。
