A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2, 6-(mesityl)2} and reversible CO addition at the Ni site
A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2, 6-(mesityl)2} and reversible CO addition at the Ni site
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DOI：
10.1073/pnas.0913399107
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发表时间：
2010-03-02
影响因子：
11.1
通讯作者：
Tatsumi, Kazuyuki
中科院分区：
文献类型：
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作者：
Ohki, Yasuhiro;Yasumura, Kazunari;Tatsumi, Kazuyuki
由四核Fe-Ni-Ni-Fe配合物[（CO）（3）Fe（mu-（SBu）-Bu-t）（3）Ni]（2）（mu-Br）（2），2与NaSDmp在-40 ℃反应，合成了一个具有畸变三角锥镍中心的[NiFe]氢化酶模型化合物，（CO）（3）Fe（mu-（SBu）-Bu-t）（3）Ni（SDmp），1（Dmp = C6H3 - 2; 6-（mesityl）（2））.发现配合物1的镍位在-40 ℃时与CO或（CNBu）-Bu-t加成，分别得到（CO）（3）Fe（（SBu）-Bu-t）（mu-（SBu）-Bu-t）（2）Ni（CO）（SDmp），3或（CO）（3）Fe（（SBu）-Bu-t）（mu-（SBu）-Bu-t）（2）Ni（（CNBu）-Bu-t）（SDmp），4.在红外光谱中，出现在2055cm（-1）处的CO带之一被指定为Ni-CO带，并且该频率与在CO抑制形式的[NiFe]氢化酶中观察到的频率相当。与[NiFe]氢化酶的CO抑制形式一样，CO在1的镍位点的配位是可逆的，而CNTBu加合物4更稳健。
A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)(3)Fe(mu-(SBu)-Bu-t)(3)Ni(SDmp), 1 (Dmp = C6H3-2; 6-(mesityl)(2)), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)(3)Fe(mu-(SBu)-Bu-t)(3)Ni](2)(mu-Br)(2), 2 with NaSDmp at -40 degrees C. The nickel site of complex 1 was found to add CO or (CNBu)-Bu-t at -40 degrees C to give (CO)(3)Fe((SBu)-Bu-t)(mu-(SBu)-Bu-t)(2)Ni(CO) (SDmp), 3, or (CO)(3)Fe((SBu)-Bu-t)(mu-(SBu)-Bu-t)(2)Ni((CNBu)-Bu-t)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055cm(-1) in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CNtBu adduct 4 is more robust.