Structural studies of trans-N2S2 copper macrocycles

Katherine D. Trotter, John Reglinski, Keith Robertson, John C. Forgie, John A. Parkinson, Alan R. Kennedy, David R. Armstrong, Rebecca J. Sowden, Corinne M. Spickett

Research output: Contribution to journalArticlepeer-review


The X-ray crystal structures of two related trans-N2S2 copper macrocycles are reported. One was isolated with the copper in the divalent form and the other with copper in its univalent form affording a valuable insight into the changes of geometry and metrical parameters that occur during redox processes in macrocyclic copper complexes. A variable temperature NMR study of the copper(I) complex is reported, indicative of a chair-boat conformational change within the alkyl chain backbone of the macrocycle. It was possible to extract the relevant kinetic and thermodynamic parameters (?G‡, 57.8 kJ mol-1; ?H‡, 52.1 kJ mol-1; ?S‡, -19.2 J K-1 mol-1) for this process at 298 K. DFT molecular orbital calculations were used to confirm these observations and to calculate the energy difference (26.2 kJmol-1) between the copper(I) macrocycle in a planar and a distorted tetrahedral disposition.
Original languageEnglish
Pages (from-to)4065-4072
Number of pages8
JournalInorganica Chimica Acta
Issue number11
Early online date3 Jun 2009
Publication statusPublished - 15 Aug 2009


  • copper
  • macrocyclic complex
  • electrochemistry
  • dynamic behaviour
  • Chemistry


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