Molecular structure of bis[(hydridotris(1-pyrazolyl)borato)copper(I)] and implications for certain copper-containing proteins
Molecular structure of bis[(hydridotris(1-pyrazolyl)borato)copper(I)] and implications for certain copper-containing proteins
复制标题
双[(氢化三(1-吡唑基)硼酸)铜(I)]的分子结构及其对某些含铜蛋白质的影响
DOI：
10.1002/chin.197506399
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发表时间：
1975
期刊：
影响因子：
--
通讯作者：
J. Ibers
中科院分区：
文献类型：
--
作者：
C. Arcus;J. Wilkinson;C. Mealli;T. Marks;J. Ibers
其中包括含铜的7·8双氧激活蛋白血青素9（一种双氧载体），酪氨酸酶10（一种加氧酶），以及可能的其他11，其中铜原子成对出现，组氨酸（咪唑）参与金属离子结合，d和还原形式涉及铜(I)。Cu [HBpz3] 12 (I)在溶液中是二聚体，并与CO反应形成羰基配合物，12·13与v （CO）反应几乎与羧血青苷反应一样低，14促使我们深入研究I的性质。我们在这里介绍了吡唑啉速率配体桥接两种金属的第一个例子，吡唑啉段也桥接两种金属，以及一种新型的流动工艺的多吡唑啉硼酸盐配合物。我们还报道了I的氧化作用，以产生我们所制定的铜氧配合物。在40℃的甲苯溶液中生长出适合衍射的I晶体。该化合物在三斜空间群P1中与一个二聚体分子在尺寸为a= 9.264 (1) Á， b= 7.638 (1) Á， c= 8.181 (1) Á， a= 92.96 (1)， ß= 101.71(1)的单晶胞中结晶。
Among these are the copper-containing, 7· 8 dioxygen-activating proteins hemocyanin9 (a dioxygen carrier), tyrosi-nase10 (an oxygenase), and possibly others11 where copper atoms occur in pairs, histidine (imidazole) is implicated in metal ion binding, 9d and a reduced form involves Cu (I). The fact that Cu [HBpz3] 12 (I) is dimeric in solution and reacts with CO to form a carbonyl complex, 12· 13 with v (CO) nearly as low as in carboxyhemocyanin, 14 has prompted us to investigate thoroughly the properties of I. We communicate here the first example of a pyrazolylbo-rate ligand bridging two metals, of the pyrazolyl segment also bridging two metals, and of a new type of fluxional pro-cess for polypyrazolylborate complexes. We also report the oxygenation of I to producewhat we formulate as a copperdioxygen complex.Crystals of I suitable fordiffraction were grown from tol-uene solution at—40 _. The compound crystallizes in the triclinic space group P1 with one dimeric molecule in a unit cell of dimensions a= 9.264 (1) Á, b= 7.638 (1) Á, c= 8.181 (1) Á, a= 92.96 (1), ß= 101.71 (1),