Exchanged Metal-Hydrogen Anagostic Bonds and Resonance of Dithiocarbamate and Thioureide Mesomers** |
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Authors: | Dr Szymon Sobczak Kinga Roszak Prof Andrzej Katrusiak |
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Institution: | Department of Materials Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland |
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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. |
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Keywords: | anagostic bond dithiocarbamate high pressure mesomers |
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