TY - JOUR
T1 - Isomeric [RuCl2(dmso)2(indazole)2] complexes: Ruthenium(II)-mediated coupling reaction of acetonitrile with 1H-indazole
AU - Reisner, Erwin
AU - Arion, Vladimir B.
AU - Rufińska, Anna
AU - Chiorescu, Ion
AU - Schmid, Wolfgang F.
AU - Keppler, Bernhard K.
N1 - CAN 143:258839 78-7 Inorganic Chemicals and Reactions Institute of Inorganic Chemistry-Bioinorganic, Environmental and Radiochemistry, Faculty of Chemistry,University of Vienna,Vienna,Austria. Journal 863307-93-1; 863307-94-2; 863307-95-3; 863459-29-4 Role: CPS (Chemical process), FMU (Formation, unclassified), PEP (Physical, engineering or chemical process), PRP (Properties), FORM (Formation, nonpreparative), PROC (Process) (elec. potential of couple contg.); 863307-90-8P; 863307-91-9P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn. and crystal structure and cyclic voltammetry of); 863459-25-0P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn. and crystal structure and optimized geometry and electronic structure and mechanism of iminoacylation on reaction with acetonitrile and cyclic voltammetry of); 863307-92-0P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and crystal structure of); 863459-27-2P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn. and optimized geometry and electronic structure and crystal structure and cyclic voltammetry of); 835616-96-1P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn. and optimized geometry and electronic structure and mechanism of iminoacylation on reaction with acetonitrile and cyclic voltammetry of); 75-05-8 (Acetonitrile) Role: RCT (Reactant), RACT (Reactant or reagent) (reactant for prepn. of ruthenium amidine chloro DMSO complexes with/without indazole); 271-44-3 (Indazole) Role: RCT (Reactant), RACT (Reactant or reagent) (reactant for prepn. of ruthenium indazole chloro DMSO complexes); 59091-96-2 (cis-Dichlorotetrakis(dimethyl sulfoxide)ruthenium) Role: RCT (Reactant), RACT (Reactant or reagent) (substitution of DMSO ligand by indazole); 245488-11-3 Role: RCT (Reactant), RACT (Reactant or reagent) (substitution of chloro ligand by DMSO)
PY - 2005/7/21
Y1 - 2005/7/21
N2 - 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}]·CH3CN (4·CH3CN) and trans,cis-[RuIICl2(dmso)2{HN=C(Me)ind}] ·H2O (5·H2O), 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. © The Royal Society of Chemistry 2005.
AB - 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}]·CH3CN (4·CH3CN) and trans,cis-[RuIICl2(dmso)2{HN=C(Me)ind}] ·H2O (5·H2O), 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. © The Royal Society of Chemistry 2005.
KW - Diastereomers (geometric
KW - prepn. and crystal structure and optimized geometry and electronic structure and cyclic voltammetry and indazole-acetonitrile coupling reaction of isomeric ruthenium DMSO indazole complexes)
KW - Acylation (mechanism
KW - metal-assisted iminoacylation of isomeric ruthenium DMSO indazole complexes on reaction with acetonitrile)
KW - Crystal structure
KW - Molecular structure
KW - Oxidation
KW - Oxidation potential (of ruthenium DMSO complexes with indazole/amidine)
KW - Molecular orbital
KW - Total energy (of ruthenium DMSO indazole isomeric complexes)
KW - Hydrogen bond (of ruthenium DMSO indazole/amidine complexes)
KW - Molecular structure (optimized
KW - of ruthenium DMSO indazole isomeric complexes)
KW - ruthenium indazole DMSO isomeric complex prepn structure coupling acetonitrile
KW - amidine ruthenium DMSO complex prepn structure
KW - crystal structure ruthenium DMSO indazole amidine complex
KW - geometry optimized ruthenium DMSO indazole isomeric complex
KW - electronic structure ruthenium DMSO indazole isomeric complex
KW - cyclic voltammetry ruthenium DMSO indazole amidine complex
KW - iminoacylation ruthenium DMSO indazole isomeric complex
UR - https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/cc8xv00&sid=DataCite
UR - https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/cc8xv33&sid=DataCite
UR - https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/cc8xv44&sid=DataCite
UR - https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/cc8xv11&sid=DataCite
UR - https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/cc8xv22&sid=DataCite
U2 - 10.1039/b503650j
DO - 10.1039/b503650j
M3 - Article
SN - 1477-9234
SP - 2355
EP - 2364
JO - Dalton Transactions
JF - Dalton Transactions
IS - 14
ER -