Magnetic susceptibility and electron spin resonance studies on amine–copper( II ) arylcarboxylates

. Can. J. Chem. 61, 2389Chem. 61, (1983.The syntheses and characterization of some ncw octaethylporphyrin complexes of ruthenium(l1) and ruthcnium(lll) are described; the complexes are Ru(OEP)(P"BU~)~. Ru(OEP)(CO)L (L = PPh3, PUBu3), [Ru(OEP)(P"BU,)~]B~, and Ru(0EP)-(PnBu3)Br, where OEP is the dianion of octaethylporphyrin. The Ru(OEP)(CO)EtOH complex, 1, which reversibly loscs the ethanol ligand in CHzC12 solution, undergoes a one-equivalent oxidation at the porphyrin ligand to gencratc the cation-radical [Ru(OEP)"(CO)]+; a purple species of 'Azu ground statc, produced electrochemically in perchlorate mcdia, can coordinate bromide to generate a green 'A,, ground state species that also results from oxidation of 1 using bromine. Coordination of pyridine to [Ru(OEP)'+CO]+ yields the Ru(OEP)"(CO)py species that can also be formcd by electrochemical oxidation of Ru(OEP)(CO)py. Addition of tertiary phosphines (PR3) to the cation-radical carbonyl spccics can lead to formation of [RU(OEP)(PR,)~]+, via an internal electron transfcr proccss from Ru(11) to the OEP" that appears to bc triggered by loss of the CO ligand. A reversible one-electron electrochemical oxidation of RU(OEP)(P"BU,)~ at 0.03 V (vs. Ag/AgCI) in CH2CIz also gives the ruthenium(Il1) biphosphine cation, while a furthcr onc-elcctron oxidation at 1.2 V generates [Ru(OEP)'+(P"BU,)~]'+, a ruthenium(lI1) n-cation radical characterized by esr. Thc [Ru(OEP)(P"Bu,),]Br complcx decomposes in the solid state to a mixture of Ru(OEP)(PUBu,)Br, formed together with free phosphine via an intramolecular ligand exchange, and RU(OEP)(P"BU~)~, formed by rcduction of the initial ionic ruthenium (lI1) [Traduit par le journal]

mentioning

confidence: 79%

Section: Materials Arld Rnethotlsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

Barley¹,

Becker²,

Domazetis³

et al. 1983

“…The other compounds were prepared by the reaction of silver (1) Infrared and electronic spectra were obtained as before (3). Magnetic susceptibilities were measured at room temperature and three different values of HdHldx using the Faraday magnetic balance described in the literature (9). The values were found to be field independent for all samples.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and structural studies of iron(II) and iron(III) sulfonates

Haynes¹,

Sams²,

Thompson³

1981

The iron(II) sulfonates Fe(CF3SO3)2 and Fe(p-CH3C6H4SO3)2 have been prepared and on the basis of vibrational and electronic spectra and magnetic and MÖssbauer data have been assigned a layer lattice structure involving hexacoordinated iron(II) and terdentate bridging anions. The FeO6 chromophore in these compounds is distorted by a trigonal elongation along the C3 axis. Fe(CH3SO3)2 has been obtained in two isomeric forms, one having a trigonal elongation of the FeO6 chromophore, the other a trigonal compression. No structural isomerism has been found for the other iron(II) sulfonates; however, evidence for such isomerism in methanesulfonates of cobalt(II) and zinc(II) is presented. While Fe(CF3SO3)2 and Fe(p-CH3C6H4SO3)2 appear to be magnetically dilute the presence of antiferromagnetic coupling in both forms of Fe(CH3SO3)2 is indicated. The iron(III) sulfonates, Fe(CF3SO3)3, Fe(p-CH3C6H4SO3)3, and Fe(CH3SO3)3, have been prepared and all three are magnetically concentrated exhibiting magnetic moments which are significantly less than 5.92 BM and which decrease with decreasing temperature.

“…Magnetic susceptibilities were measured at room temperature at three different values of H dH/dx with a Faraday magnetic balance (33). No field dependence was observed for any of the complexes.…”

Section: Magnetic Susceptibilitiesmentioning

confidence: 99%

Structural, magnetic, and spectroscopic studies of tetrakis(pyridine) complexes of iron(II) sulfonates

Haynes¹,

Rettig²,

Sams³

et al. 1986

. 64, 429 (1986).The iron(I1) complexes Fe(NC5H5)4(RS03)2 where R = CF3, CH,, and p-CH3C6H4 have been prepared and their crystal structures determined by single crystal X-ray diffraction. Cryst$ of trans-bis(methanesulfonato-O)tetrakis(pyridine)iron(II) are monoclinic, a = 16.524(2), b = 9.1 127(6), c = 18.684(2) A, P = 109.903(6)", Z = 4, space group Pn. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.034 and R,, = 0.038 for 4243 reflections with I 2 3u(4. Crystals of trans-bis(trifluoromethanesulfonato-O)tetrakis(pyridine)iron(II) are monoclinic, a = 10.456(1), b = 9.2981(8), c = 14.625(2) A, P = 96.372(6)", Z = 2, space group Pn. Structure solved and refined as above to R = 0.036, and R,, = 0.037 for 1483 reflections with 1 2 3u(4. Crystals of transbis(p-toluenesulfonato-O)tetrakis(pyridine)iron(II) are orthorhombic, a = 40.818(2), b = 9.8722(6), c = 17.3544(7) A, Z = 8, space group Fdd2. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to R = 0.030 and R,, = 0.032 for 1851 reflections with 1 2 3u(l). All three structures show discrete octahedral molecules with monodentate trans-coordinated sulfonate groups. Two crystallographically independent molecules are observed in the R = CH3 structure, the difference between them involving the orientation of the CH3S03 groups with respect to the 0-Fe-0 vector. The FeN402 chromophore in each compoundo is a tetragonally compressed octahedron (approximate D4,, Dans le trois structures, on retrouve des molCcules octaCdriques individuelles avec des groupements sulfonates monodentates coordonntes en trans. Dans la structure oh R=CH3, on observe deux moltcules qui sont cristallographiquement indtpendantes; la difftrence entre les deux implique I'orientation des groupements CH3S03 par rapport au vecteur 0-Fe-0.Dans chacun des composts, le chromophore FeN402 est un octatdre qui est comprimt d'une faqon tttragonale (symttrie approximative D4)!) et dans lequel les distances Fe-N moyennes sont 2,21, 2.23 et 2,24 A alors que les distances Fe---0 sont 2,11, 2,06 et 2,08 a respectivement pour les derives CF3, CH3 et p-CH3C6H4. On a CtudiC les composts en faisant appel aux spectroscopies vibrationnelles, tlectroniques et de Mossbauer, i des mesures de susceptibilitt magnttique et i la calorimttrie de balayage difftrentiel. Les valeurs des dtdoublements quadrupolaires obtenus a partir des spectres de Mossbauer indiquent que les trois composts existent dans un ttat fondamental 5B2,; on a analysC les donnCes de susceptibilitC magnttique (de 3 10a 4,2 K) i l'aide des modtles tant de champ cristallin que de dtdoublement i champ ztro en faisant I'hypothtse que 1'Ctat fondamental est bien celui-18.[Traduit par le journal] IntroductionWe had earlier utilized spectroscopic and magnetic techThe study of the coordinating properties of sulfonate anions, niques to investigate the coordination of Sulfonate anions in RS03-, is of interest for a number of re...