Exchanged Metal-Hydrogen Anagostic Bonds and Resonance of Dithiocarbamate and Thioureide Mesomers

Szymon Sobczak; Kinga Roszak; Andrzej Katrusiak

doi:10.1002/chem.202201235

Exchanged Metal-Hydrogen Anagostic Bonds and Resonance of Dithiocarbamate and Thioureide Mesomers

Chemistry. 2022 Aug 10;28(45):e202201235. doi: 10.1002/chem.202201235. Epub 2022 Jun 23.

Authors

Szymon Sobczak¹, Kinga Roszak¹, Andrzej Katrusiak¹

Affiliation

¹ Department of Materials Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614, Poznań, Poland.

PMID: 35638134
DOI: 10.1002/chem.202201235

Abstract

The pressure-induced transformation of plane-square complex nickel(II) bis(N,N-diethyldithiocarbamate) between its soft dithiocarbamate (form I) and thioureide (form II) mesomeres is coupled to the interchange of anagostic Ni⋅⋅⋅H-C interactions from methylene to the methyl group, respectively. At 1.23 GPa, the clearly visible giant anomalous compressibility of the crystal reveals a potential-energy difference of 5.4 kJ mol^-1 between the two complex forms. The structural and spectroscopic results, which are supported by quantum-mechanical calculations, connect this solid-state phase transition with the mesomeric transition, and this is accompanied by the conformational transformation of anagostic Ni⋅⋅⋅H-C rearrangement and formation of the charge-assisted S^- ⋅⋅⋅H-C bond under pressure.

Keywords: anagostic bond; dithiocarbamate; high pressure; mesomers.