Show simple item record

dc.contributor.authorBelousoff, Matthew J.
dc.contributor.authorBattle, Andrew R.
dc.contributor.authorGraham, Bim
dc.contributor.authorSpiccia, Leone
dc.date.accessioned2017-05-03T16:04:25Z
dc.date.available2017-05-03T16:04:25Z
dc.date.issued2007
dc.date.modified2014-04-09T00:40:34Z
dc.identifier.issn0277-5387
dc.identifier.doi10.1016/j.poly.2006.06.029
dc.identifier.urihttp://hdl.handle.net/10072/58003
dc.description.abstractA series of new asymmetrically N-substituted derivatives of the 1,4,7-triazacyclononane (tacn) macrocycle have been prepared from the common precursor 1,4,7-triazatricyclo[5.2.1.04,10]decane: 1-ethyl-4-isopropyl-1,4,7-triazacyclononane (L1), 1-isopropyl-4-propyl-1,4,7-triazacyclononane (L2), 1-(3-aminopropyl)-4-benzyl-7-isopropyl-1,4,7-triazacyclononane (L3), 1-benzyl-4-isopropyl-1,4,7-triazacyclononane (L4) and 1,4-bis(3-aminopropyl)-7-isopropyl-1,4,7-triazacyclononane (L5). The corresponding monomeric copper(II) complexes were synthesised and were found to be of composition: [Cu(L1)Cl2] · 1/2 H2O (C1), [Cu(L4)Cl2] · 4H2O (C2), [Cu(L3)(MeCN)](ClO4)2 (C3), [Cu(L5)](ClO4)2 · MeCN · NaClO4 (C4) and [Cu(L2)Cl2] · 1/2 H2O (C5). The X-ray crystal structures of each complex revealed a distorted square-pyramidal copper(II) geometry, with the nitrogen donors on the ligands occupying 3 (C1 and C2), 4 (C3) or 5 (C4) coordination sites on the Cu(II) centre. The metal complexes were tested for the ability to hydrolytically cleave phosphate esters at near physiological conditions, using the model phosphodiester, bis(p-nitrophenyl)phosphate (BNPP). The observed rate constants for BNPP cleavage followed the order kC1 ≈ kC2 > kC5 ≫ kC3 > kC4, confirming that tacn-type Cu(II) complexes efficiently accelerate phosphate ester hydrolysis by being able to bind phosphate esters and also form the nucleophile necessary to carry out intramolecular cleavage. Complexes C1 and C2, featuring asymmetrically disubstituted ligands, exhibited rate constants of the same order of magnitude as those reported for the Cu(II) complexes of symmetrically tri-N-alkylated tacn ligands (k ∼ 1.5 × 10−5 s−1).
dc.description.peerreviewedYes
dc.description.publicationstatusYes
dc.languageEnglish
dc.language.isoeng
dc.publisherElsevier
dc.publisher.placeUnited Kingdom
dc.relation.ispartofstudentpublicationN
dc.relation.ispartofpagefrom344
dc.relation.ispartofpageto355
dc.relation.ispartofissue2
dc.relation.ispartofjournalPolyhedron
dc.relation.ispartofvolume26
dc.rights.retentionY
dc.subject.fieldofresearchTransition Metal Chemistry
dc.subject.fieldofresearchInorganic Chemistry
dc.subject.fieldofresearchPhysical Chemistry (incl. Structural)
dc.subject.fieldofresearchOther Chemical Sciences
dc.subject.fieldofresearchcode030207
dc.subject.fieldofresearchcode0302
dc.subject.fieldofresearchcode0306
dc.subject.fieldofresearchcode0399
dc.titleSyntheses, structures and hydrolytic properties of copper(II) complexes of asymmetrically N-functionalised 1,4,7-triazacyclononane ligands
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.date.issued2007
gro.hasfulltextNo Full Text
gro.griffith.authorBattle, Andrew


Files in this item

FilesSizeFormatView

There are no files associated with this item.

This item appears in the following Collection(s)

  • Journal articles
    Contains articles published by Griffith authors in scholarly journals.

Show simple item record