To the top

Page Manager: Webmaster
Last update: 9/11/2012 3:13 PM

Tell a friend about this page
Print version

A Versatile Dinucleating … - University of Gothenburg, Sweden Till startsida
Sitemap
To content Read more about how we use cookies on gu.se

A Versatile Dinucleating Ligand Containing Sulfonamide Groups

Journal article
Authors J. Sundberg
H. Witt
L. Cameron
Mikael Håkansson
J. Bendix
C. J. McKenzie
Published in Inorganic Chemistry
Volume 53
Issue 6
Pages 2873-2882
ISSN 0020-1669
Publication year 2014
Published at Department of Chemistry and Molecular Biology
Pages 2873-2882
Language en
Links dx.doi.org/10.1021/ic402599e
Keywords metal-amide bond, magnetic-properties, crystal-structures, molecular-structure, copper(ii) complex, hydroxo, binding, arylsulfonylnitrene, insertion, valence, apman rl, 1980, inorganica chimica acta-articles, v43, p29
Subject categories Chemical Sciences

Abstract

Copper, iron, and gallium coordination chemistries of the new pentadentate bis-sulfonamide ligand 2,6-bis(N-2-pyridylmethylsulfonamido)-4-methylphenol (psmpH(3)) were investigated. PsmpH(3) is capable of varying degrees of deprotonation, and notably, complexes containing the fully trideprotonated ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu-2(psmp)(OH)] and [Cu-2(psmp)(OAc)(2)](-), demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent flexibility since additional one- and three-atom bridging ligands bridge the two copper(11) ions in each complex, respectively. This gives rise to a difference of 0.4 angstrom in the Cu center dot center dot center dot Cu distances. Complexes with 2:3 and 2:1 ligand/metal stoithiometries for the divalent and trivalent metal ions, respectively, were observed in [Cu-3(psmp)(2)(H2O)] and [M(psmpH)(psmpH(2))], where M = Ga-III, Fe-III. The deprotonated tridentate N-2-pyridylsulfonylmethylphenolato moieties chelate the metal ions in a meridional fashion, whereas in [Cu-3(psmp)(2)(H2O)] the rare mu(2)-N-sulfonarnido bridging coordination mode is observed. In the bis-ligand mononuclear complexes, one picolyl arm of each ligand is protonated and uncoordinated. Magnetic susceptibility measurements on the doubly and triply bridged dicopper(II) complexes indicate strong and medium strength antiferromagnetic coupling interactions, with J = 234 cm(-1) and 115 cm(-1) for [Cu-2(psmp)(OH)] and [Cu-2(psmp)(OAc)(2)](-), respectively (in H-HDvV = ... +JS(1)S(2) convention). The trinudear [Cu-3(psmp)(2)(H2O)], in which the central copper ion is linked to two flanking copper atoms by two mu(2)-N-sulfonamido bridges and two phenoxide bridges shows an overall magnetic behavior of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry densityfunctional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm(-1).

Page Manager: Webmaster|Last update: 9/11/2012
Share:

The University of Gothenburg uses cookies to provide you with the best possible user experience. By continuing on this website, you approve of our use of cookies.  What are cookies?