Related Experiment Video
Updated: May 17, 2026

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
meso-Thiaporphyrinoids revisited: missing of sulfur by small metals
Hiroki Kamiya1, Takeshi Kondo, Takafumi Sakida
1Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan.
Abstract:
Facile synthesis of meso-aryl-substituted 5,15-dithiaporphyrins and 10-thiacorroles has been achieved by sulfidation of α,α'-dichlorodipyrrin metal complexes with sodium sulfide in DMF. Thiacorrole metal complexes exhibit distinct aromaticity due to 18 π-conjugation including the lone pair on sulfur, whereas dithiaporphyrins are nonaromatic judging from (1)H NMR spectra, X-ray analysis, and absorption spectra. We have found that Ni(II) and Al(III) dithiaporphyrin complexes undergo smooth thermal sulfur extrusion reaction to give the corresponding thiacorrole complexes, whereas free base, Zn(II), Pd(II), and Pt(II) dithiaporphyrin complexes did not exhibit the similar reactivity. The DFT calculations have elucidated a reaction pathway involving an episulfide intermediate, which can explain the markedly different reactivity among dithiaporphyrin metal complexes.
More Related Videos
14:44Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
Related Concept Videos
Sulfur Assimilation
Preparation and Reactions of Sulfides
Structure and Nomenclature of Thiols and Sulfides
Microbes and the Sulfur Cycle
Imperfections in Crystal Structure: Non-Stoichiometric Defects
Preparation and Reactions of Thiols