Structural studies of trans-N2S2 copper macrocycles

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Trotter, K.D. and Reglinski, J. and Robertson, K. and Forgie, J.C. and Parkinson, J.A. and Kennedy, A.R. and Armstrong, D.R. and Sowden, R.J. and Spickett, C.M. (2009) Structural studies of trans-N2S2 copper macrocycles. Inorganica Chimica Acta, 362 (11). pp. 4065-4072. ISSN 0020-1693 (http://dx.doi.org/10.1016/j.ica.2009.05.060)

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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.

ORCID iDs

Trotter, K.D., Reglinski, J. ORCID logoORCID: https://orcid.org/0000-0002-0263-4168, Robertson, K., Forgie, J.C., Parkinson, J.A. ORCID logoORCID: https://orcid.org/0000-0003-4270-6135, Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Armstrong, D.R., Sowden, R.J. and Spickett, C.M.;
CORE (COnnecting REpositories)