Insertion reactions of CS2, COS, and PhNCS at thiolate-bridged diiron centers
Insertion reactions of CS2, COS, and PhNCS at thiolate-bridged diiron centers
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CS2、COS 和 PhNCS 在硫醇桥联铁中心的插入反应
DOI：
10.1039/b920144k
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发表时间：
2010-01-01
影响因子：
4
通讯作者：
Qu, Jingping
中科院分区：
文献类型：
--
作者：
Chen, Yanhui;Peng, Ying;Qu, Jingping
用 CS2 处理 [Cp*Fe(mu(2)-SR)(3)FeCp*] (1a, R = Et; 1b, R = Me)，以优异的产率获得插入产物 [Cp*Fe(mu(2)-SR)(2)(mu-eta(2)- S2CSR)FeCp*] (2a, R = Et; 2b, R = Me)，并保留 Fe2S2 亚基。图2a和2b代表CS2活化和掺入二铁-SR键的第一个例子。 [Cp*Fe(mu(2)-SEt) 2(mu-eta(2)-S-2)FeCp*] (3) 由 COS 和 1a 通过 COS 的脱羰和硫偶合反应制备，从而形成 S-2(2-) 配体。将 PhNCS 添加到 1a 中得到单核复合物 [Cp*Fe(SEt)(eta(2)-SC(SEt)NPh)] (4)。 1a被发现对CO2不发生反应。还描述了插入产物的光谱表征、X 射线衍射分析和电化学。
Treatment of [Cp*Fe(mu(2)-SR)(3)FeCp*] (1a, R = Et; 1b, R = Me) with CS2 obtains the insertion products [Cp*Fe(mu(2)-SR)(2)(mu-eta(2)- S2CSR)FeCp*] (2a, R = Et; 2b, R = Me) with the retained Fe2S2 subunit in excellent yield. 2a and 2b represent the first examples for the CS2 activation and incorporation at the diiron-SR bond. [Cp*Fe(mu(2)-SEt) 2(mu-eta(2)-S-2)FeCp*] (3) is prepared from COS and 1a through the decarbonylation and sulfur coupling reaction of COS resulting in the formation of S-2(2-) ligand. Addition of PhNCS into 1a affords a mononuclear complex [Cp*Fe(SEt)(eta(2)-SC(SEt)NPh)] (4). 1a is found to be unreactive towards CO2. The spectral characterization, X-ray diffraction analysis, and electrochemistry of the insertion products have also been described.