Nonenzymic nitrogen fixation by an iron-molybdenum model for nitrogenase.
Nonenzymic nitrogen fixation by an iron-molybdenum model for nitrogenase.
复制标题
固氮酶铁钼模型的非酶固氮。
DOI：
10.1021/ja00785a063
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发表时间：
1973
影响因子：
15
通讯作者：
J. Miller
中科院分区：
文献类型：
--
作者：
E. E. Van Temelen;J. Gladysz;J. Miller
将38 THF溶液（0.4 mmol / 100ml）缓慢加入含有2等量4和8等量萘化钠（NaNp）的溶液中，在室温下搅拌反应混合物20小时。可见和红外光谱分析表明，在加入3.9之前，NaNp已经完全消耗。在加入20%的HC1水溶液后，除去11溶剂，用H20从残渣中提取NH4C1。nesler试验呈阳性，凯氏定氮法测定的NH3产率12范围为0.013 ~ 0.044 mmol/mmol(3.13)，用NH3气体电极测定的氨产率14下降到凯氏定氮法测定的水平的至少85%。以上述方法还原3时，在16等量NaNp的存在下，NH3的产率高达0.268 mmol /mmol。发现了新的N2固定物，这些固定物与3和4的反应途径有关。Mo配合物3本身，虽然在金属Mg或Na-Hg存在下产生，但4ab被过量的NaNp还原为氨（0.100-0.300 mmol NH3/mmol 3）， [Mo (N2) 2 (dppe) 2]+ Ir 13（0.040-0.085）。
After the slow addition of a THF solution of 38 (0.4 mmol in 100 ml) to a solution containing 2 equiv of 4 and 8 equiv of sodium naphthalenide (NaNp), all at room temperature, the reaction mixture was allowed to stir for 20 hr. Visible and infrared spectroscopy indicated that the NaNp was completely consumed prior to the addition of 3.9 After the addition of 20% aqueous HC1, 11 solvent was removed and the NH4C1 was extracted from the residue with H20. Nessler tests were positive, and the NH3 yields as determined by the Kjeldahl method12 ranged from 0.013 to 0.044 mmol/mmol of 3.13 Ammonia yields were also mea-sured using an NH3 gas electrode, 14 and fell at levels at least 85% of those determined by the Kjeldahl method. When a reduction of 3 was carried out as above, but in the presence of 16 equiv of NaNp, the yield rose to as high as 0.268 mmol of NH3/mmol of 3. Additional novel N2 fixations were uncovered which bear on the reaction pathway involving 3 and 4. The Mo complex 3 itself, although produced in thepresence of metallic Mg or Na-Hg, 4ab is reducible by excess NaNp to ammonia (0.100-0.300 mmol of NH3/mmol of 3) as are [Mo (N2) 2 (dppe) 2]+ Ir 13 (0.040-0.085)