Issue 18, 2002

Synthesis and coordination chemistry of 1,4,7,10,13-pentakis(2-hydroxyethyl)-1,4,7,10,13-pentaazacyclopentadecane: a five armed pendant donor macrocycle

Abstract

Synthesis of the five armed pendant donor macrocycle 1,4,7,10,13-pentakis(2-hydroxyethyl)-1,4,7,10,13-pentaazacyclopentadecane (phec15) has been achieved by reaction of 1,4,7,10,13-pentaazacyclopentadecane ([15]aneN5) with ethylene oxide in the absence of light and oxygen over an eight day period. The first three pKa values for phec15 have been determined by potentiometric titration (I = 0.1 mol dm−3 NEt4ClO4) to be 8.51 ± 0.01, 7.57 ± 0.01 and 3.74 ± 0.01, respectively, and the final two are < 2.3. The stability constants (log(K/dm3 mol−1) for [M(phec15]2+ complexes in aqueous solution where M = Co(II), Cu(II), Zn(II), Cd(II) and Pb(II) are 7.45 ± 0.03, 14.69 ± 0.02, 8.47 ± 0.01, 12.57 ± 0.03, and 10.35 ± 0.03, respectively. Gas phase ab initio modelling predicts that phec15 adopts the trans-I configuration, by virtue of linked hydrogen bonding between the five pendant hydroxyl groups, and that [Ba(phec15)]2+ and [Sr(phec15)]2+ are ten coordinate with an approximately pentagonal prismatic structure in which the plane of the five oxygen atoms is rotated either clockwise or anticlockwise with respect to the nitrogen atom plane, giving rise to Λ and Δ enantiomers, respectively. Variable temperature 13C{1H} NMR spectra support these structural predictions and in the case of [Ba(phec15)]2+ complete lineshape analysis gave the kinetic parameters k = (4.0 ± 0.3) × 104 s−1, ΔH = 45.4 ± 2.2 kJ mol−1 and ΔS = −4.5 ± 8.5 J K−1 mol−1 for intramolecular exchange between the Λ and Δ forms. Gas phase ab initio modelling and 13C{1H} NMR spectra indicate that [Cd(phec15)]2+ is most probably six coordinate with an approximately trigonal prismatic N3O3 donor atom set arising from coordination of non-adjacent nitrogen atoms and their associated pendant hydroxyl groups.

Graphical abstract: Synthesis and coordination chemistry of 1,4,7,10,13-pentakis(2-hydroxyethyl)-1,4,7,10,13-pentaazacyclopentadecane: a five armed pendant donor macrocycle

Article information

Article type
Paper
Submitted
12 Jun 2002
Accepted
07 Aug 2002
First published
20 Aug 2002

J. Chem. Soc., Dalton Trans., 2002, 3571-3577

Synthesis and coordination chemistry of 1,4,7,10,13-pentakis(2-hydroxyethyl)-1,4,7,10,13-pentaazacyclopentadecane: a five armed pendant donor macrocycle

K. M. Walters, M. A. Buntine, S. F. Lincoln and K. P. Wainwright, J. Chem. Soc., Dalton Trans., 2002, 3571 DOI: 10.1039/B205700J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements