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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Structural characterization of the picket fence (TpivPP) porphyrins Co(TpivPP), Co(TpivPP)(NO2)(1-MeIm), and Co(TpivPP)(NO2)(1,2-Me(2)Im)
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Structural characterization of the picket fence (TpivPP) porphyrins Co(TpivPP), Co(TpivPP)(NO2)(1-MeIm), and Co(TpivPP)(NO2)(1,2-Me(2)Im)

机译：栅栏（TpivPP）卟啉Co（TpivPP），Co（TpivPP）（NO2）（1-MeIm）和Co（TpivPP）（NO2）（1,2-Me（2）Im）的结构表征

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The compounds Co(TpivPP) (1), Co(TpivPP)(NO2)(1 -MeIm) (2), and Co(TpivPP)(NO2)(1,2-Me(2)Im) (3) have been synthesized (TpivPP = meso-tetrakis(alpha,alpha,alpha,alpha-o-pivalamidophenyl)porphyrinto dianion), and their structures have been determined with single-crystal X-ray diffraction methods, 1: a = 17.578(1) Angstrom, b = 17.596(1) Angstrom, c = 20.639(1) Angstrom,Angstrom, beta = 115.03(1)degrees, P2(1)/c, Z = 4, T = -120 degrees C. 2: a = 18.522(4) Angstrom, b =18.942(4) Angstrom, c = 18.177(4) Angstrom, beta = 90.68(3)degrees, C2/c, Z = 4, T = -70 degrees C. 3: a = 18.998(4) Angstrom, b = 19.187(4) Angstrom, c = 18.000(4) Angstrom, beta = 90.96(3)degrees, C2/c, Z = 4, T = -120 degrees C. Compounds 2 and 3 have crystallographically imposed 2-fold axes. In 2 and 3, which represent R-state (relaxed) and T-state (tense) models, respectively, for hemoglobin, the NO2 ligand is bound on the "picket" side to the Co atom, and either 1-MeIm (for 2) or 1,2-Me(2)Im (for 3) is bound to the Co atom at the sixth coordination site on the sterically unhindered side of the molecule. The average deviations of atoms from the 24-atom porphyrin core are 0.031, 0.129, and 0.117 Angstrom for 1, 2, and 3, respectively. The Co atom is -0.043(1) Angstrom out of the mean 24-atom porphyrin plane toward the 1-MeIm ligand in 2 and -0.089(1) Angstrom out of the plane toward the 1,2-Me(2)Im ligand in 3. The bonds of both axial ligands in the R-state model 2, 1.898(4) Angstrom for Co-N(O-2) and 1.995(4) Angstrom for Co-N(base), are shorter than the corresponding bonds in the T-state model 3, 1.917(4) Angstrom for Co-N(O-2) and 2.091(4) Angstrom for Co-N(base). [References: 65]
机译：化合物Co（TpivPP）（1），Co（TpivPP）（NO2）（1-MeIm）（2）和Co（TpivPP）（NO2）（1,2-Me（2）Im）（3）已合成（TpivPP =内消旋四（α，α，α，α-o-新戊酰胺基苯基）卟啉二价阴离子），其结构已通过单晶X射线衍射法确定：1 a = 17.578（1）埃b = 17.596（1）埃，c = 20.639（1）埃，埃，beta = 115.03（1）度，P2（1）/ c，Z = 4，T = -120摄氏度2：a = 18.522（ 4）埃，b = 18.942（4）埃，c = 18.177（4）埃，beta = 90.68（3）度，C2 / c，Z = 4，T = -70摄氏度3：a = 18.998（4 ）埃，b = 19.187（4）埃，c = 18.000（4）埃，beta = 90.96（3）度，C2 / c，Z = 4，T = -120摄氏度。化合物2和3的晶体学性质为2折轴。在2和3中，分别代表血红蛋白的R态（松弛）模型和T态（紧张）模型，NO2配体在Co原子的“小齿”侧结合，并且与1-MeIm结合（对于2）或1,2-Me（2）Im（对于3）在分子的空间不受阻碍的一侧的第六个配位点处与Co原子结合。原子与24原子卟啉核的平均偏差分别为1,2和3分别为0.031、0.129和0.117埃。 Co原子在平均24原子卟啉平面内朝向2中的1-MeIm配体为-0.043（1）埃，在平面上朝向1,2-Me（2）Im配体而言为-0.089（1）埃在3中。在R状态模型2中，两个轴向配体的键对于Co-N（O-2）为1.898（4）埃，对于Co-N（碱）为1.995（4）埃比相应的短。在T态模型3中，Co-N（O-2）为1.917（4）埃，Co-N（碱）为2.091（4）埃。 [参考：65]

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