Redox-coupled complexation of 23-phospha-21-thiaporphyrin with group 10 metals: a convenient access to stable core-modified isophlorin-metal complexes.
Redox-coupled complexation of 23-phospha-21-thiaporphyrin with group 10 metals: a convenient access to stable core-modified isophlorin-metal complexes.
复制标题
DOI：
10.1021/ja807742g
复制
发表时间：
2008-11
影响因子：
15
通讯作者：
Y. Matano;Takashi Nakabuchi;S. Fujishige;H. Nakano;H. Imahori
中科院分区：
文献类型：
--
作者：
Y. Matano;Takashi Nakabuchi;S. Fujishige;H. Nakano;H. Imahori
采用P，S， n2杂化卟啉与零价钯、镍和铂的氧化还原偶联络合制备了核修饰的异氯啉-金属配合物。在这一转变过程中，核磷原子由于具有较高的P−M亲和力，在增强18π卟啉环的电子接受能力和稳定20π异磷啉环方面起着至关重要的作用。分离的Pd和Pt配合物在环境条件下具有化学稳定性。用x射线晶体学对Pd−P，S，N2异氯啉配合物进行了结构表征，发现该配合物为一个扭曲的20π平面，中心为方形平面钯（II）。实验（1H， UV - vis和x射线）和理论（密度泛函理论计算）结果表明，P，S， n2 -异氯啉-金属配合物在磁性和几何尺度上都具有非芳构性。
Core-modified isophlorin−metal complexes were successfully prepared by redox-coupled complexation of P,S,N2-hybrid porphyrin with zerovalent palladium, nickel, and platinum. In this transformation, the core-phosphorus atom plays crucial roles in enhancing the electron-accepting ability of the 18π porphyrin ring and stabilizing the 20π isophlorin ring owing to high P−M affinity. The isolated Pd and Pt complexes are chemically stable under ambient conditions. The Pd−P,S,N2 isophlorin complex was structurally characterized by X-ray crystallography, which revealed a distorted 20π plane with a square planar palladium(II) center. Experimental (1H, UV−vis, and X-ray) and theoretical (density functional theory calculations) results suggest that the P,S,N2-isophlorin−metal complexes possess nonaromaticity in terms of both magnetic and geometrical criteria.