Santiago Cabaleiro

Electrochemical synthesis of nickel(II) complexes of tosylamides: crystal structures of [(4-methylphenyl)sulfonyl]-imino-1H-pyridine], 2,2′-bipyridine bis{[(4-methylphenyl) sulfonyl]-2-pyridyl-amide}nickel(II) and 1,10-phenanthroline bis{[(4-methylphenyl) sulfonyl]-2-pyridyl-amide}nickel(II)

The complex [NiL2] has been synthesised by the electrochemical oxidation of nickel in an acetonitrile solution of [(4-methylphenyl)sulfonyl]-imino-1H-pyridine (HL). When the oxidation was carried out in the presence of neutral ligands L′ (pyridine, 2,2′-bipyridine or 1,10-phenanthroline) the complexes [NiL2py2], [NiL2bipy] and [NiL2phen] were obtained. The crystal structures of [(4-methylphenyl)sulfonyl]-imino-1H-pyridine, 2,2′-bipyridine bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}nickel(II) and 1,10-phenanthroline bis{[(4-methylphenyl) sulfonyl]-2-pyridyl-amide}nickel(II) were determined by X-ray diffraction methods. In the monomeric complexes, the nickel atom is in a distorted octahedral environment defined by the amide and pyridyl nitrogen atoms of the two ligands and the two bipyridine or phenanthroline nitrogen atoms. The vibrational and electronic spectra of the complexes are discussed and are shown to agree with the structures.

Direct electrochemical synthesis of cobalt(II) complexes of tosylamides: crystal structures of [CoL2py2], [CoL2DMF2], [CoL2bipy] and [CoL2phen], L=[(4-methylphenyl)sulfonyl]-2-pyridylamide

Abstract Several complexes with tosylamides were synthesised by the electrochemical oxidation of cobalt in an acetonitrile solution of [(4-methylphenyl)sulfonyl]-imino-1H-pyridine (HL) and the appropriate neutral coligand: L′ (pyridine, 2,2′-bipyridine, 1,10-phenanthroline or N,N-dimethylformamide). The structures of bis-(N,N-dimethylformamide)bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cobalt(II), bis-(pyridine)bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cobalt(II), 2,2′-bipyridine bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cobalt(II) and 1,10-phenanthroline bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cobalt(II) were determined by X-ray diffraction methods. In these monomeric complexes, the cobalt atom is in a distorted octahedral environment. The vibrational and electronic spectra of the complexes are discussed and are shown to agree with the structures.

Cadmium(II) complexes with [(4-methylphenyl)sulfonyl]-2-pyridyl-amine: crystal structures of bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cadmium(II); aquo-bis(pyridine) bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cadmium(II) and 1,10-phenanthroline bis{[(4-methylphenyl)sulfonyl]-2-pyridyl-amide}cadmium(II)

Abstract Electrochemical oxidation of cadmium in a solution of [(4-methylphenyl)sulfonyl]-2-pyridyl-amine (HL) in acetonitrile/dichloromethane afforded the compound [CdL2]. When pyridine (py), 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrolytic phase, [CdL2py2(H2O)], [CdL2bipy] and [CdL2phen] were obtained. The crystal structures of [CdL2] (1), [CdL2py2(H2O)] (2) and [CdL2phen] (3) have been determined by X-ray diffraction techniques. The complex [CdL2] is best described in terms of a linear polymer with the metal atom in a [CdN4O2] distorted octahedral environment. The [CdL2py2(H2O)] and [CdL2phen] complexes are monomeric, with the cadmium atoms in [CdN6O] distorted pentagonal bipyramid and [CdN6] trigonal prismatic environments, respectively.

Electrochemical Synthesis and Characterization of Zinc(II) Complexes with [(4-Methylphenyl)Sulfonyl]-1H-Amido-2-Phenyl-2-Oxazolines†

A series of [(4-methylphenyl)sulfonyl]-1H-amido-2-phenyl-2-oxazoline ligands, HTs-ROz, has been synthesized by the reaction of substituted 2-(2-aminophenyl)oxazolines and p-toluensulfonyl chloride. The electrochemical oxidation of a sacrificial zinc anode in an acetonitrile solution of the corresponding ligand gave compounds of general formula [Zn(Ts-ROz)2]. All complexes have been characterized by microanalysis, IR and 1H NMR spectroscopy and single-crystal X-ray diffraction. In all cases, the metal atom is coordinated by the nitrogen atoms of two monoanionic ligands. spectros-Elektrochemische Synthese und Charakterisierung von Zink(II)-Komplexen mit [(4-Methylphenyl)sulfonyl]-1H-amido-2-phenyl-2-oxazolinen complexes; Crystal structure Eine Serie von [(4-Methylphenyl)sulfonyl]-1H-amido-2-phenyl-2-oxazolin-Liganden HTs-ROz wurden durch Reaktion von substituierten 2-(2-Aminophenyl)oxazolinen mit p-Toluolsulfonylchlorid synthetisiert. Die elektrochemische Oxidation von Opfer-Zink-Anoden in Acetonitrillosungen der entsprechenden Liganden fuhrt zu Verbindungen der Formel [Zn(Ts-ROz)2]. Alle Komplexe wurden durch Mikroanalysen, IR- und 1H-NMR-Spektren und durch Einkristall-Strukturanalysen charakterisiert. In allen Fallen sind die Metallatome durch die N-Atome zweier monoanionischer Liganden koordiniert.

Electrochemical synthesis, X-ray diffraction and spectroscopic characterisation of Co(II) compounds with [(4-methylphenyl)sulfonyl]-1H-imino-2-phenyl-2-oxazolines

Abstract The electrochemical oxidation of anodic cobalt in acetonitrile solutions of [(4-methylphenyl)sulfonyl]-1H-imino-2-phenyl-2-oxazoline ligands, [HTsROz], affords compounds of general formula [Co(TsROz)2]. All complexes have been characterised by microanalysis, IR and UV–Vis spectroscopy, magnetic measurements and, in the cases of HTs4iPrOz, [Co(TsOz)2], [Co(Ts4MeOz)2], [Co(Ts4iPrOz)2] and [Co(Ts4EtOz)2], by single-crystal X-ray diffraction.

Synthesis, characterization and structures of the novel rhenium(IV) complexes trans-[ReCl4{PPh2(OMe)}2], trans-[ReCl4{PPh2(OEt)}2] and trans-[ReCl4(OPPh3)2]

Abstract trans-Tetrachlorobis(methyl-diphenylphosphinite)rhenium(IV) and trans-tetrachlorobis(ethyl-diphenylphosphinite)rhenium(IV) were obtained by recrystallization of the corresponding rhenium(III) phosphinite complexes, [ReCl3L3], in chlorinated solvents. The structures of the compounds consist of discrete molecules with trans-octahedral coordination geometry around the rhenium atom, having Re–P distances between 2.534(1) and 2.555(2) A and Re–Cl distances in the range 2.321(1)–2.336(1) A. trans-[ReCl4(OPPh3)2] is formed during the reaction of triphenyloxonium tetrafluoroborate with [ReNCl2(PPh3)2]. P–O bond lengths of 2.033(4) A have been found, while the Re–Cl bonds are 2.336(2) and 2.344(2) A, respectively.

Copper(II) [(4-methylphenyl)sulfonyl]-1H-imino-(2-phenyl-2-oxazoline) complexes

Neutral copper complexes of the deprotonated [(4-methylphenyl)sulfonyl]-1H-imino-(2-phenyl-2-oxazoline) proligands, [HTs-ROz], R = H, 5-Me, 4-Me, 4-Et, 4-iPr, have been prepared by electrochemical oxidation of anodic copper in an MeCN solution of the corresponding proligand. The [Cu(Ts-ROz)2] complexes were characterised by microanalysis, i.r. and electronic spectroscopies, and by e.p.r. and magnetic measurements. The crystal structures of HTs-5MeOz, [Cu(Ts-Oz)2], [Cu(Ts-5MeOz)2] and [Cu(Ts-4MeOz)2] were determined by X-ray diffraction.