Structural studies of trans-N2S2 copper macrocycles |
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Authors: | Katherine D Trotter Keith Robertson John A Parkinson David R Armstrong Corinne M Spickett |
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Institution: | a Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK b Strathclyde Institute of Pharmacy and Biomedical Sciences, University of Strathclyde, 27 Taylor Street, Glasgow, G4 0NR, UK |
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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. |
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Keywords: | Copper Macrocyclic complex Electrochemistry Dynamic behaviour |
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