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New Chlorido(dimethyl sulfoxide)iridium(III) Complexes with N 6 ‐Substituted Adenines – Kinetic N(7) versus Thermodynamic N(9) Coordinated Adenine Isomers
Author(s) -
GarcíaRaso Angel,
Fiol Juan J.,
Albertí Francisca M.,
Lagos Yolanda,
Torres Marta,
BarcelóOliver Miquel,
Prieto María J.,
Moreno Virtudes,
Mata Ignasi,
Molins Elies,
Estarellas Carolina,
Frontera Antonio,
Quiñonero David,
Deyà Pere M.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000821
Subject(s) - chemistry , iridium , protonation , coordination sphere , dimethyl sulfoxide , crystallography , sulfoxide , metal , octahedron , molecule , ligand (biochemistry) , coordination complex , octahedral molecular geometry , crystal structure , medicinal chemistry , stereochemistry , catalysis , ion , organic chemistry , biochemistry , receptor
New chlorido(dimethyl sulfoxide)iridium(III) complexes with N 6 ‐substituted adenine derivatives: [Ir III Cl 4 (DMSO‐κS){H‐AdeC x –κN(7)}] · n H 2 O [ x = 3, n = 3 for 1 ; x = 4, n = 0.5 and 3 for 2a and 2b , respectively; x = 5, n = 0 for 3 ; x = 10, n = 0.33 for 4 ] and [Ir III Cl 4 (DMSO‐κS){H‐AdeC x –κN(9)}] [ x = 3 for 5 ; x = 4 for 6 , x = 5 for 7 ; x = 10 for 8 ] have been synthesized and characterized by spectroscopic techniques and by single‐crystal X‐ray diffraction studies ( 1 , 2b and 5 ). In all cases, iridium shows octahedral geometry and is coordinated to four chlorido ligands and one S atom from dimethyl sulfoxide (DMSO‐κS). The coordination sphere of the metal is completed by the N 6 ‐substituted adenine molecule. Two different coordination modes are observed: (i) the ligand is protonated at N(1) and coordinated through N(7) (complexes 1 – 4 ); (ii) the adenine is protonated at N(3) and coordinated through N(9) (complexes 5 – 8 ). The kinetic/thermodynamic mechanisms that yield the different coordination products have been studied by using DFT calculations. Electrophoretic mobility studies and atomic force microscopy (AFM) investigation of the interaction between complexes 1 , 5 , 8 and plasmid pBR322 DNA have been performed.