Structural studies of trans-N2S2 copper macrocycles

K.D. Trotter, J. Reglinski, K. Robertson, J.C. Forgie, J.A. Parkinson, A.R. Kennedy, D.R. Armstrong, R.J. Sowden, C.M. Spickett

Research output: Contribution to journalArticle

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Abstract

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 (ΔG‡, 57.8 kJ mol−1; ΔH‡, 52.1 kJ mol−1; ΔS‡, −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.
LanguageEnglish
Pages4065-4072
Number of pages7
JournalInorganica Chimica Acta
Volume362
Issue number11
DOIs
Publication statusPublished - 15 Aug 2009

Fingerprint

Copper
copper
Orbital calculations
boats
Boats
Molecular orbitals
Discrete Fourier transforms
seats
molecular orbitals
Crystal structure
Nuclear magnetic resonance
Thermodynamics
X rays
thermodynamics
nuclear magnetic resonance
crystal structure
Kinetics
Geometry
kinetics
geometry

Keywords

  • copper
  • macrocyclic complex
  • electrochemistry
  • dynamic behaviour

Cite this

Trotter, K. D., Reglinski, J., Robertson, K., Forgie, J. C., Parkinson, J. A., Kennedy, A. R., ... Spickett, C. M. (2009). Structural studies of trans-N2S2 copper macrocycles. Inorganica Chimica Acta, 362(11), 4065-4072. https://doi.org/10.1016/j.ica.2009.05.060
Trotter, K.D. ; Reglinski, J. ; Robertson, K. ; Forgie, J.C. ; Parkinson, J.A. ; Kennedy, A.R. ; Armstrong, D.R. ; Sowden, R.J. ; Spickett, C.M. / Structural studies of trans-N2S2 copper macrocycles. In: Inorganica Chimica Acta. 2009 ; Vol. 362, No. 11. pp. 4065-4072.
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Trotter, KD, Reglinski, J, Robertson, K, Forgie, JC, Parkinson, JA, Kennedy, AR, Armstrong, DR, Sowden, RJ & Spickett, CM 2009, 'Structural studies of trans-N2S2 copper macrocycles' Inorganica Chimica Acta, vol. 362, no. 11, pp. 4065-4072. https://doi.org/10.1016/j.ica.2009.05.060

Structural studies of trans-N2S2 copper macrocycles. / Trotter, K.D.; Reglinski, J.; Robertson, K.; Forgie, J.C.; Parkinson, J.A.; Kennedy, A.R.; Armstrong, D.R.; Sowden, R.J.; Spickett, C.M.

In: Inorganica Chimica Acta, Vol. 362, No. 11, 15.08.2009, p. 4065-4072.

Research output: Contribution to journalArticle

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T1 - Structural studies of trans-N2S2 copper macrocycles

AU - Trotter, K.D.

AU - Reglinski, J.

AU - Robertson, K.

AU - Forgie, J.C.

AU - Parkinson, J.A.

AU - Kennedy, A.R.

AU - Armstrong, D.R.

AU - Sowden, R.J.

AU - Spickett, C.M.

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PY - 2009/8/15

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N2 - 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 (ΔG‡, 57.8 kJ mol−1; ΔH‡, 52.1 kJ mol−1; ΔS‡, −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.

AB - 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 (ΔG‡, 57.8 kJ mol−1; ΔH‡, 52.1 kJ mol−1; ΔS‡, −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.

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KW - electrochemistry

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