Stereochemistry of manganese porphyrins. 3. Molecular stereochemistry of alpha,beta,gamma,delta-tetraphenylporphinato-(1-methylimidazole)manganese(II)1,2.
Stereochemistry of manganese porphyrins. 3. Molecular stereochemistry of alpha,beta,gamma,delta-tetraphenylporphinato-(1-methylimidazole)manganese(II)1,2.
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DOI：
10.1021/ja00450a025
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发表时间：
1977-04
影响因子：
15
通讯作者：
Kirner Jf;Reed Ch;S. Wr
中科院分区：
文献类型：
--
作者：
Kirner Jf;Reed Ch;S. Wr
a,/3, 7, 5-Tetraphenylporphinato (l-methylimidazole) manganese (II) crystallizes as the tetrahydrofuran solvate in the monoclinic system, space group P2\¡ n. The unit cell has a= 27.405 (7) Á, b= 9.645 (5) Á, and c= 17.768 (9) Á, and ß= 112.45 (2), and contains four molecules. The calculated and experimental densities are 1.258 and 1.27 g/cm3, respectively, at 20±1 C. Measurement of diffracted intensities employed scans with graphite-monochromated Mo Ka radiation on a Syntex four-circle diffractometer. All independent reflections for (sin)/< 0.626 Á-1 were measured; 5276 reflections were retained as observed. These data were employed in the determinationof structure using the heavy-atom method and block-di-agonal least-squares refinement of the 540 structural parameters. The final conventionaland weighted discrepancy factors are 0.052 and 0.061, respectively. The structural parameters of the square-pyramidal MnNs coordination group reflects the large size of the high-spin manganese (II) atom; the average equatorial Mn-N distance is 2.128 Á and the axial Mn-N bond distance is 2.192 Á. The manganese atom is displaced 0.56 Á from the mean skeletal plane. The relevance of this structure to deoxyhemoglobin and manganese-substituted deoxyhemoglobin is discussed.The stereochemistry of high-spin manganese (II) porphy-rins, the isoelectronic high-spin iron (III) and the high-spin iron (II) porphyrins are expected to be dominated by the large size of the metal atom. This large size should yield derivatives in which the metal atom is substantially out of the porphyrin plane. We report herein the molecular stereochemistry of a five-coordinate high-spin manganese (II) derivative, a,(3, 7, 6-tetraphenylporphinato (1-methylimidazole) manganese (II), to be written as Mn (l-MeIm)(TPP). 4 We compare the molecular stereochemistry of Mn (l-MeIm)(TPP) with other five-coordinate metalloporphyrin derivatives including
