Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases.
Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases.
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DOI：
10.1039/c0dt00909a
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发表时间：
2011-01
影响因子：
4
通讯作者：
Li-Cheng Song;Zhao-Jun Xie;Xufeng Liu;Jiang-Bo Ming;Jian-Hua Ge;Xiao-Guang Zhang;Tianhai Yan;Peng Gao
中科院分区：
文献类型：
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作者：
Li-Cheng Song;Zhao-Jun Xie;Xufeng Liu;Jiang-Bo Ming;Jian-Hua Ge;Xiao-Guang Zhang;Tianhai Yan;Peng Gao
以母体配合物[μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A)为起始物，合成了一系列新的偶氮二硫酸二铁（ADT）配合物（1-8），可作为[FeFe]氢化酶的活性位点模型。丙二酰氯乙基或二氯丙二酰氯在吡啶存在下对A进行处理，得到含丙二酰配合物[(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6)(1)和[Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2)(2)。1和2的进一步处理与PPh(3)在不同条件下产生了PPh(3)代替复合物[(μ原理图(2)(2)NCH (2) CH (2) O (2) CCH(2)有限公司(2)等]Fe (2) (CO) (5) (PPh(3))(3),((μ原理图(2)(2)NCH (2) CH (2) O (2) CCH(2)有限公司(2)等]Fe (2) (CO) (4) (PPh(3))(2)(4)和(Fe (2) (CO) (5) (PPh(3))(μ原理图(2)(2)NCH (2) CH (2) O (2) C] (2) CH(2)(5)。更有趣的是，配合物1-3可以在CBr(4)和1,8-重氮双环[5.4.0]十一-7-烯（DBU）存在下与C（60）通过Bingel-Hirsch反应生成含C（60）的配合物[(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60))(7)和[(μ-SCH(2) (2)NCH(2) O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3))(8)。新的adt型模型1-8通过元素分析和光谱学进行了表征，2-4通过x射线晶体学进行了进一步研究，6-8通过DFT方法进行了详细研究。
A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.