Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie Street, 50-383 Wrocław, Poland.
Inorg Chem. 2012 Mar 5;51(5):3247-60. doi: 10.1021/ic2027175. Epub 2012 Feb 22.
3,18-Diphenyl-8,13-di-p-tolyl-20-thiaethyneporphyrin ([18]thiatriphyrin(4.1.1)), which formally contains an C1-C2 ethyne moiety instead of pyrrole embedded in the macrocyclic framework of 21-thiaporphyrin, was obtained in a modification of the "3 + 1" approach using the ethyne analogue of tripyrrane (1,4-diphenyl-1,4-di(pyrrol-2-yl)but-2-yne) and 2,5-bis(p-tolylhydroxymethyl)thiophene. The spectroscopic and structural properties of 20-thiaethyneporphyrin reflect its macrocyclic aromaticity, revealing a combination of the acetylene (≥C-C≡C-C≤) and cumulene (>C═C═C═C<) character of the C18-C1-C2-C3 linker. The magnetic manifestations of aromaticity and antiaromaticity of thiaethyneporphyrin and its two-electron-oxidized derivative were observed using (1)H NMR spectroscopy and were confirmed by density functional theory calculations involving chemical shifts and nucleus-independent chemical shift analysis. Protonation of 20-thiaethyneporphyrin yielded a nonaromatic tautomer of iso-20-thiaethyneporphyrin, locating the saturated meso carbon adjacent to thiophene. Insertion of palladium(II) and nickel(II) into 20-thiaethyneporphyrin afforded planar palladium(II) thiaethyneporphyrin and low-spin diamagnetic nickel(II) 20-thiaethyneporphyrin as determined by X-ray crystallography. 20-Thiaethyneporphyrin acts as a dianionic ligand that coordinates through the two nitrogen and one sulfur donors. Metal(II) ions are uniquely exposed to form an intramolecular metal(II)-η(2)-CC bond, whereas the organometallic fragment is coplanar with the whole macrocycle. Coordination of pyridine converts diamagnetic nickel(II) thiaethyneporphyrin into its paramagnetic counterpart as determined by (1)H NMR.
3,18-二苯基-8,13-二对甲苯基-20-硫代乙炔卟啉([18]噻三角卟啉(4.1.1))，其形式上包含一个 C1-C2 乙炔部分，而不是嵌入 21-噻卟啉大环框架中的吡咯，是通过三吡咯烷的乙炔类似物(1,4-二苯基-1,4-二(吡咯-2-基)丁-2-炔)和 2,5-双(对甲苯基羟甲基)噻吩的“3+1”方法进行修饰得到的。20-硫代乙炔卟啉的光谱和结构性质反映了其大环芳香性，显示出 C18-C1-C2-C3 键合的乙炔(≥C-C≡C-C≤)和累积烯(>C═C═C═C<)特征的结合。使用(1)H NMR 光谱观察到硫代乙炔卟啉及其二电子氧化衍生物的芳香性和反芳香性的磁表现，并通过涉及化学位移和核独立化学位移分析的密度泛函理论计算进行了确认。20-硫代乙炔卟啉的质子化生成了非芳香性的异-20-硫代乙炔卟啉的互变异构体，使饱和的中碳原子与噻吩相邻。钯(II)和镍(II)插入 20-硫代乙炔卟啉中得到平面钯(II)硫代乙炔卟啉和低自旋反磁性镍(II)20-硫代乙炔卟啉，这是通过 X 射线晶体学确定的。20-硫代乙炔卟啉作为二价阴离子配体通过两个氮和一个硫供体配位。金属(II)离子独特地暴露形成一个分子内金属(II)-η(2)-CC 键，而有机金属片段与整个大环共面。吡啶的配位将反磁性镍(II)硫代乙炔卟啉转化为顺磁性对应物，这是通过(1)H NMR 确定的。
