Isomeric [RuCl2(dmso)2(indazole)2] complexes: Ruthenium(II)-mediated coupling reaction of acetonitrile with 1H-indazole

Author(s)
Erwin Reisner, Vladimir Arion, Anna Rufinska, Ion Chiorescu, Wolfgang Schmid, Bernhard Keppler
Abstract

Reaction of the antitumor complex trans-[RuIIICl 4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans- [RuIICl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[RuIICl2(dmso) 2(Hind)2] (2) and cis,cis,cis-[RuIICl 2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[RuIICl2(dmso)4] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[RuIICl2(dmso) (Hind){HN=C(Me)ind}]žCH3CN (4žCH3CN) and trans,cis-[RuIICl2(dmso)2{HN=C(Me)ind}] žH2O (5žH2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C=N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry. Œ The Royal Society of Chemistry 2005.

Organisation(s)
Department of Inorganic Chemistry, Department of Physical Chemistry
External organisation(s)
Max-Planck-Institut für Kohlenforschung
Journal
Dalton Transactions
Pages
2355-2364
No. of pages
10
ISSN
1477-9226
Publication date
2005
Peer reviewed
Yes
Austrian Fields of Science 2012
1040 Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/2dd07c62-764d-42c7-8a81-90e6deb87ee1