Novel Ruthenium Phthalocyanine-Containing Model Complex for the Active Site of [FeFe]-Hydrogenases: Synthesis, Structural Characterization, and Catalytic H2 Evolution
Novel Ruthenium Phthalocyanine-Containing Model Complex for the Active Site of [FeFe]-Hydrogenases: Synthesis, Structural Characterization, and Catalytic H2 Evolution
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DOI：
10.1021/acs.organomet.5b01040
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发表时间：
2016-03
期刊：
影响因子：
2.8
通讯作者：
Li-Cheng Song;Fei-Xian Luo;Bei-bei Liu;Z. Gu;Hao Tan
中科院分区：
文献类型：
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作者：
Li-Cheng Song;Fei-Xian Luo;Bei-bei Liu;Z. Gu;Hao Tan
采用多步合成法合成了第一个含酞菁大环的[FeFe]氢化酶模型配合物（i-BuO）8 PcRu（CO）（μ-PDT）[（Ph 2 P）2NCH 2C 5 H4 N] Fe 2（CO）4（6）. 4-吡啶甲基胺与Ph_2PCl/Et_3N在CH_2Cl_2中室温反应得到4-吡啶甲基取代的氮杂二膦（Ph_2P）_2NCH_2C_5H_4N（1），而1与二铁络合物（μ-PDT）Fe_2（CO）_6在邻二甲苯中进一步反应得到4-吡啶甲基氮杂二膦螯合的二铁络合物（μ-PDT）[（Ph_2P）_2NCH_2C_5H_4N] Fe_2（CO）_4（2）。3，6-二羟基邻苯二甲腈在DMF中与i-BuBr/K2 CO 3在80 °C下反应得到3，6-二异丁氧基邻苯二甲腈3，3与锂丝在Na 2SO 4中进一步反应得到异丁氧基酞菁（i-BuO）8 PcH 2（4）。4与Ru_3（CO）_（12）在1，4-二苯甲酮中反应，得到钌酞菁（i-BuO）_8PcRu（CO）_2（5）。最后，在Me 3 NO存在下，在CH 2Cl 2中，5与二铁络合物2的CO取代反应导致目标模型络合物6的形成。段时间...
The first phthalocyanine (Pc) macrocycle-containing [FeFe]-hydrogenase model complex, (i-BuO)8PcRu(CO)(μ-PDT)[(Ph2P)2NCH2C5H4N]Fe2(CO)4 (6), has been prepared by a multistep synthetic route. The treatment of 4-picolylamine with Ph2PCl/Et3N in CH2Cl2 at room temperature gave 4-picolyl-substituted azadiphosphine (Ph2P)2NCH2C5H4N (1), whereas further treatment of 1 with diiron complex (μ-PDT)Fe2(CO)6 in refluxing o-xylene produced the 4-picolylazadiphosphine-chelated diiron complex (μ-PDT)[(Ph2P)2NCH2C5H4N]Fe2(CO)4 (2). While 3,6-dihydroxyphthalonitrile reacted with i-BuBr/K2CO3 in DMF at 80 °C to give 3,6-diisobutoxyphthalonitrile 3, further reaction of 3 with lithium wire in refluxing i-BuOH afforded isobutoxyphthalocyanine (i-BuO)8PcH2 (4). Furthermore, 4 reacted with Ru3(CO)12 in refluxing PhCN to give ruthenium phthalocyanine (i-BuO)8PcRu(CO)2 (5). Finally, CO substitution reaction of 5 with diiron complex 2 in the presence of Me3NO in CH2Cl2 resulted in formation of the targeted model complex 6. While ...