Metal-Porphyrin Orbital Interactions in Paramagnetic Iron Complexes Having Planar and Deformed Porphyrin Ring.
Metal-Porphyrin Orbital Interactions in Paramagnetic Iron Complexes Having Planar and Deformed Porphyrin Ring.
复制标题
具有平面和变形卟啉环的顺磁性铁配合物中的金属-卟啉轨道相互作用。
DOI：
10.1002/jccs.201200474
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
M. Takahashi
中科院分区：
文献类型：
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作者：
M. Nakamura;A. Ikezaki;M. Takahashi
铁卟啉配合物的~ 1H和~（13）CNMR化学位移主要由顺磁性铁3d与卟啉分子轨道相互作用引起的周围碳、氮原子的自旋密度决定。本文综述了铁的半占据3d轨道如dπ（dxz，dyz），dxy，d和d-如何与特定的卟啉分子轨道相互作用，并影响平面，褶皱，鞍形和圆顶配合物的1H和13 C NMR化学位移。揭示轨道相互作用和NMR化学位移之间的关系对于确定合成的铁卟啉络合物以及天然存在的血红素蛋白的精细电子结构是非常重要的。
1H and13C NMR chemical shifts of iron porphyrin complexes are determined mainly by the spin densities at the peripheral carbon and nitrogen atoms caused by the interaction between paramagnetic iron 3d and porphyrin molecular orbitals. This review describes how the half‐occupied iron 3d orbitals such as dπ(dxz, dyz), dxy, d, and d‐ interact with a specific porphyrin molecular orbital and affect the1H and13C NMR chemical shifts in planar, ruffled, saddled, and domed complexes. Revealing the relationship between the orbital interactions and NMR chemical shifts is quite important to determine the fine electronic structures of synthetic iron porphyrin complexes as well as naturally occurring heme proteins.