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 journalArticle

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 (?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.
LanguageEnglish
Pages4065-4072
Number of pages8
JournalInorganica Chimica Acta
Volume362
Issue number11
Early online date3 Jun 2009
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
  • Chemistry

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

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

Research output: Contribution to journalArticle

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AU - Trotter, Katherine D.

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AU - Robertson, Keith

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AU - Parkinson, John A.

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AU - Armstrong, David R.

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AU - Spickett, Corinne M.

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Trotter KD, Reglinski J, Robertson K, Forgie JC, Parkinson JA, Kennedy AR et al. Structural studies of trans-N2S2 copper macrocycles. Inorganica Chimica Acta. 2009 Aug 15;362(11):4065-4072. https://doi.org/10.1016/j.ica.2009.05.060