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Updated: Jun 15, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Selective synthesis of the missing tiara-like Ni10, Ni5 and Ni6 thiolates by the C-S bond cleavage of bis(thioether)
Suparno Debnath1, Sandip Giri1, Ganesan Mani1
1Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302 India. gmani@chem.iitkgp.ac.in.
Abstract:
A series of new bis(phenylthioether) and bis(benzylthioether) compounds (L1-L5) having hexahydropyrimidine, imidazolidine and dihydroperimidine backbones were synthesized. Instead of giving NHC complexes, these compounds undergo facile C-S bond cleavages upon treatment with Ni(II) salts to selectively give new toroidal Ni(II) thiolates: [Ni10(SPh)20] (1) and [Ni5(SCH2Ph)10] (5), and the known [Ni6(SCH2Ph)12] (8), as confirmed by single crystal X-ray diffraction studies. By-products such as RSSR (R = Ph and CH2Ph) and partially C-S bond cleaved starting compounds were isolated or detected as well from these reactions. The C-S bond cleavage does not take place with L5 having the dihydroperimidine backbone and a plausible mechanism is proposed based on by-products isolated or detected. DFT calculations give insights into the electronic structures of these ring systems and the nature of bonding with which a dichloromethane is present inside the cavity of 1. Experimentally observed absorption spectra of 1, 5 and 8 match with the calculated spectra.
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