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Issue 9, 2005
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Conformational dynamics of Cu(I) complexes of tripodal ligands: steric control of molecular motion

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Abstract

The dynamics of molecular conformational changes for Cu(I) complexes of two tripodal ligands were studied. Variable-temperature NMR and circular dichroism in combination with two-dimensional NMR experiments were employed to determine the structural and energetic details of a dynamic process in which one of three arms dissociates from coordination to Cu(I). Dissociation was triggered by addition of a strongly coordinating anion (SCN). One-electron oxidation to the Cu(II) complex returned coordination of all three ligand arms. The observed phenomena were dependent upon steric crowding; addition of a single methyl group to one arm resulted in marked differences in behavior. The CuSCN and CuPF6 complexes of tris(2-quinolylmethyl)amine (TQA) and the CuPF6 complex of 1-(quinolin-2-yl)-N,N-bis(quinolin-2-ylmethyl)ethanamine (MeTQA) did not give any evidence for differences in coordination over the temperature range 0–35 °C, while CuI(MeTQA)NCS demonstrated marked differences in NMR but not CD spectra over this temperature range. In the latter complex, two diastereotopic arms displace each other with a transition energy of 14.0 kcal mol−1. The structure of the arm-dissociated complex contains a higher degree of stereochemical complexity than the tetradentate complexes.

Graphical abstract: Conformational dynamics of Cu(i) complexes of tripodal ligands: steric control of molecular motion

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Publication details

The article was received on 27 Jun 2005, accepted on 18 Jul 2005 and first published on 04 Aug 2005


Article type: Paper
DOI: 10.1039/B509050D
Citation: New J. Chem., 2005,29, 1147-1151
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    Conformational dynamics of Cu(I) complexes of tripodal ligands: steric control of molecular motion

    J. Zhang, K. Siu, C. H. Lin and J. W. Canary, New J. Chem., 2005, 29, 1147
    DOI: 10.1039/B509050D

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