Wydział Chemii

Elżbieta S. Nojman

Anna Berlicka

Ludmiła Szterenberg

Lechosław Latos-Grażyński

2012

Inorganic Chemistry

51

3247-3260

10.1021/ic2027175

Naukowa

Angielski

Artykuł

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 ¹H 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)−η²-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 ¹H NMR.

https://doi.org/10.1021/ic2027175

https://www.acs.org/content/acs/en.html