Comparison of the Structures of the Five-Coordinate Cobalt(II)Pyridine, Five-Coordinate Cobalt(III) Methyl, and Six-Coordinate Cobalt(III) Methyl Pyridine Complexes of Octaethylporphyrin
Comparison of the Structures of the Five-Coordinate Cobalt(II)Pyridine, Five-Coordinate Cobalt(III) Methyl, and Six-Coordinate Cobalt(III) Methyl Pyridine Complexes of Octaethylporphyrin
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八乙基卟啉五配位吡啶钴、五配位甲基钴(III)和六配位甲基吡啶钴配合物的结构比较
DOI：
10.1021/ja00095a022
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发表时间：
1994
影响因子：
15
通讯作者：
A. M. Stolzenberg
中科院分区：
文献类型：
--
作者：
J. Summers;J. L. Petersen;A. M. Stolzenberg
通过X射线衍射测定了Co(OEP)CH3、Co(OEP)(CH3)(Py)和Co(OEP)(DMAP)配合物的分子结构。这些复合物通过反应序列彼此相关并与辅酶B] 3 相关，该反应序列涉及吡啶与五配位烷基-Co(III)卟啉复合物的配位以提供六配位烷基-Co(III)卟啉吡啶复合物，随后烷基-钴键均裂以提供五配位Co(II)卟啉吡啶复合物。化合物 (2, 3, 7, 8, 12, 13, 17, 18-八乙基卟啉)(4-.(jV, fV,-二甲氨基)吡啶)钴(II), Co (OEP)(DMAP)，在单斜空间群 P2\/n (Z= 4) 中结晶，晶胞尺寸 a= 14.392 (6) A, b= 14.864 (6) A、c= 18.217 (5) A、ß=95.60 (3) 和 V= 3878.4 (2.6) A* 123。基于 /> 0 的 5122 次反射，结构被细化为 F02 上的 R= 0.050。1.982 (2)-A Co—N «、距离和钴原子从卟啉氮平面的 0.12-A 位移是钴 (II) 卟啉与含氮碱基的五配位、方形锥体配合物的典型特征，但 2.191 (2)-A Co-Na 距离比之前观察到的吡啶轴向配体更长。化合物(2,3,7,8,12,13,17,18-八乙基卟啉)-(甲基)钴(III),Co(OEP)CH3，在三斜空间群(Z=4)中每个不对称单元结晶有两个独立分子，晶胞尺寸a=13.776(1)A，b=14.038(2)A， c= 16.593 (2) A, a=
The molecular structures of the complexes of Co (OEP) CH3, Co (OEP)(CH3)(Py), and Co (OEP)(DMAP) were determined by X-ray diffraction. The complexes are related to each other and to coenzyme B] 3 by a reaction sequence that involves coordinationof pyridine to the five-coordinate alkyl-Co (III) porphyrin complex to afford a six-coordinate alkyl-Co (III) porphyrin pyridine complex followed by homolysis of the alkyl-cobalt bondto afford a five-coordinate Co (II) porphyrin pyridine complex. The compound (2, 3, 7, 8, 12, 13, 17, 18-octaethylporphyrinato)(4-.(jV, fV,-dimethylamino) pyridine) cobalt (II), Co (OEP)(DMAP), crystallized in the monoclinic space group P2\/n (Z= 4) with unit celldimensions a= 14.392 (6) A, b= 14.864 (6) A, c= 18.217 (5) A, ß=95.60 (3), and V= 3878.4 (2.6) A* 123. The structure was refined to R= 0.050 on F02 on the basis of 5122 reflections with/> 0. The 1.982 (2)-A Co—N «, distance and the 0.12-A displacement of the cobalt atom from the porphyrin nitrogen plane are typical of five-coordinate, square-pyramidal complexes of cobalt (II) porphyrins with nitrogenous bases, but the 2.191 (2)-A Co—Na, distance is longer than previously observed for a pyridine axial ligand. The compound (2, 3, 7, 8, 12, 13, 17, 18-octaethylporphyrinato)-(methyl) cobalt (III), Co (OEP) CH3, crystallized with two independent molecules per asymmetric unit in the triclinic space group(Z= 4) and had unit celldimensions a= 13.776 (1) A, b= 14.038 (2) A, c= 16.593 (2) A, a=