Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
Proc Natl Acad Sci U S A. 2010 Mar 2;107(9):3994-7. doi: 10.1073/pnas.0913399107. Epub 2010 Feb 10.
A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)(3)Fe(micro-S(t)Bu)(3)Ni(SDmp), 1 (Dmp = C(6)H(3)-2,6-(mesityl)(2)), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex (CO)(3)Fe(micro-S(t)Bu)(3)Ni(micro-Br)(2), 2 with NaSDmp at -40 degrees C. The nickel site of complex 1 was found to add CO or CN(t)Bu at -40 degrees C to give (CO)(3)Fe(S(t)Bu)(micro-S(t)Bu)(2)Ni(CO)(SDmp), 3, or (CO)(3)Fe(S(t)Bu)(micro-S(t)Bu)(2)Ni(CN(t)Bu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm(-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 CN(t)Bu adduct 4 is more robust.
具有扭曲三角双锥镍中心的 [NiFe] 氢化酶模型化合物 (CO)(3)Fe(micro-S(t)Bu)(3)Ni(SDmp)，1（Dmp = C(6)H(3)-2,6-(mesityl)(2)），是通过四核 Fe-Ni-Ni-Fe 配合物 (CO)(3)Fe(micro-S(t)Bu)(3)Ni(micro-Br)(2)，2 与 NaSDmp 在-40°C 下反应合成的。发现配合物 1 的镍位在-40°C 下可添加 CO 或 CN(t)Bu，分别得到(CO)(3)Fe(S(t)Bu)(micro-S(t)Bu)(2)Ni(CO)(SDmp)，3，或(CO)(3)Fe(S(t)Bu)(micro-S(t)Bu)(2)Ni(CN(t)Bu)(SDmp)，4。3 的红外光谱中出现在 2055 cm(-1)处的一个 CO 带被指定为 Ni-CO 带，该频率与 [NiFe] 氢化酶的 CO 抑制形式观察到的频率相当。与 [NiFe] 氢化酶的 CO 抑制形式一样，1 中镍位的 CO 配位是可逆的，而 CN(t)Bu 加合物 4 则更稳定。
