State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 30007, China.
Dalton Trans. 2011 Jan 28;40(4):837-46. doi: 10.1039/c0dt00909a. Epub 2010 Dec 9.
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)CCH(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)CCH(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)CC(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.
一系列新的二铁氮杂二硫代（ADT）配合物（1-8）已经被合成，这些配合物可以被视为 [FeFe]氢化酶的活性位点模型，它们是从母体配合物[(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A)开始合成的。在吡啶存在下，用乙基丙二酰氯或丙二酰二氯处理 A 可以得到含有丙二酰基的配合物[(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)CCH(2) (2)。进一步用 PPh(3)处理 1 和 2 在不同条件下产生了 PPh(3)取代的配合物[(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)和 Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2) (5)。更有趣的是，配合物 1-3 可以在 CBr(4)和 1,8-二氮杂双环[5.4.0]十一-7-烯 (DBU)存在下与 C(60)反应，通过 Bingel-Hirsch 反应得到含有 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)CC(C(60)) (7)和 [(μ-SCH(2))(2)NCH(2)CH(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，而 2-4 则通过 X 射线晶体学进一步研究，6-8 通过 DFT 方法进行了详细研究。
