STRUCTURAL CHARACTERIZATION OF ZINC(II) COMPLEXES OF OCTAETHYLOXOPHLORIN DIANION AND OCTAETHYLOXOPHLORIN RADICAL-ANION
STRUCTURAL CHARACTERIZATION OF ZINC(II) COMPLEXES OF OCTAETHYLOXOPHLORIN DIANION AND OCTAETHYLOXOPHLORIN RADICAL-ANION
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DOI：
10.1021/ja00035a032
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发表时间：
1992-04-22
影响因子：
15
通讯作者：
ZOVINKA, EP
中科院分区：
文献类型：
--
作者：
BALCH, AL;NOLL, BC;ZOVINKA, EP
锌(II)的八乙氧基膦二阴离子络合物锌(II)(OEPOH)易溶于吡啶(Py)，形成对空气敏感的红色溶液，从该溶液中分离出结晶的{(Py)Zn(II)(OEPOH..py)}。X-射线晶体结构表明存在一个五配位的锌和一个轴向的吡啶配体和一个平面的氧杂多酚大环。中位羟基取代基与第二个吡啶氢键。锌(II)的红色吡啶溶液(OEPOH)氧化得到绿色溶液，从绿色溶液中分离出稳定的自由基络合物{(Py)Zn(II)(OEPO.)}(Py)。X-射线晶体结构表明，锌(II)离子为五配位的单轴吡啶配体。第二个未配位的吡啶被捕获在恶膦自由基的另一侧。该结构存在典型的五配位卟啉配合物的反转无序和中位氧取代基的无序。比较了这两种密切相关的物质的晶体堆积，它们只有一个电子和一个质子不同。
The zinc(II) complex of octaethyloxophlorin dianion, Zn(II)(OEPOH), readily dissolves in pyridine (py) to form red, air-sensitive solutions from which crystalline {(py)Zn(II)(OEPOH..py)} has been isolated. The X-ray crystal structure reveals the presence of a five-coordinate zinc with an axial pyridine ligand and a planar oxophlorin macrocycle. The meso-hydroxyl substituent is hydrogen bonded to a second pyridine. Oxidation of red pyridine solutions of Zn(II)(OEPOH) gives green solutions from which crystals of the stable free radical complex {(py)Zn(II)(OEPO.)}(py) have been isolated. The X-ray crystal structure shows that the zinc(II) ion is five-coordinate with a single axial pyridine ligand. A second, uncoordinated pyridine is trapped on the opposite side of the oxophlorin radical. The structure suffers from inversion disorder as is typical for five-coordinate porphyrin complexes and from disorder of the meso-oxo substituent. The crystal packings of these two closely related substances, which differ only by an electron and a proton, are compared.