The electronic structure of μ-pyrazinedecaamminediruthenium(5+) p-toluenesulfonate

Creutz, Carol; Good, Mary L.; Chandra, Subhas

doi:10.1016/0020-1650(73)80050-9

Cited by 28 publications

(50 citation statements)

References 6 publications

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“…Thus, although electron transfer is known to be fast at room temperature, on the time scale of "Ru Móssbauer spectroscopy (ca. 10" s) valences are trapped at 4 K. 28 The same types of information which we have obtained for the mixed-valence iron acetate are, in principle, obtainable from temperature-dependent "Ru Móssbauer spectroscopy. Unfortunately, low recoil-free fractions preclude the observation of "Ru Móssbauer spectra at temperatures where thermally activated electron transfer is facile.…”

Section: Resultssupporting

confidence: 60%

Magnetic and spectroscopic properties of FeIIFeIII2(CH3CO2)6L3, L = water or pyridine. Direct observation of the thermal barrier to electron transfer in a mixed-valance complex

Dziobkowski¹,

Wrobleski²,

Brown³

1981

Inorg. Chem.

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The mixed-valence iron (I1, 111,111) acetates [Fe@(CH3C02)&3], where L = water or pyridine, have been prepared and studied by M&bauer, infrared, and optical spectroscopy and magnetic susceptibility methods. Variabletemperature magnetic susceptibility data for the aquo complex are interpreted on the basis of an HDVV S2 = 2, SI = S3 = 5 / 2 spin-exchange model with JI2 = JZ3 = -50.0 cm-I and J13 = -14.5 crn-'. An intervalence-transfer band is observed at 13 800 cm-' in the room-temperature electronic spectrum of the aquo complex. MBssbauer spectra of these compounds are markedly temperature dependent. At 17 K absorptions due to distinct Fe(I1) and Fe(II1) sites are observed while at 300 K a single absorption is observed. Spectra at intermediate temperatures are modeled by assuming intratrimer electronic relaxation between pairs of iron ions. The activation energy for relaxation derived from this model is 470 cm-' for the aquo complex. This energy is equal to the barrier to intramolecular, intervalence thermal electron transfer. IntroductionMany transition-metal ions form carboxylate complexes

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Section: Resultssupporting

confidence: 60%

Magnetic and spectroscopic properties of FeIIFeIII2(CH3CO2)6L3, L = water or pyridine. Direct observation of the thermal barrier to electron transfer in a mixed-valance complex

Dziobkowski¹,

Wrobleski²,

Brown³

1981

Inorg. Chem.

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“…

The results of the variable-temperature magnetic susceptibility, EPR, and NMR experiments on salts of [((N EOs-Ru)2pyr]"+ ( = 4, 5, 6) and on a salt of [((NEDsRulpyr]3* are presented. The unpaired electron in the mixed valence [2,3] oxidation state of the dimer is localized in a (d.vz, d^z) orbital on the Ru(lll) center. The electron from the Ru(ll) center is transferred through the pyrazine bridge to the other metal site at a rate which is fast on the NMR time scale, but slow on the EPR time scale.

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confidence: 99%

“…[2,3] - [3,2] the current theories of electron transfer phenomena. Although many workers have attempted to obtain such rate data for the thermal electron transfer process, the experimental conditions appropriate for observing the phenomenon as a dynamic process have not been found.…”

mentioning

confidence: 99%

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Experimental evidence for trapped valences in the mixed-valence complex .mu.-pyrazine-bis(pentaammineruthenium) tosylate. Electron paramagnetic resonance, magnetic susceptibility, and nuclear magnetic resonance results

Bunker¹,

Drago²,

Hendrickson³

et al. 1978

J. Am. Chem. Soc.

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“…[4][5][6][7] For mixed-valence ions, intervalence transfer (IT) bands are often observed.1"-12 From the properties of IT bands, it is possible to estimate both the extent of metal-metal interaction in the ground state and the rate of thermal electron transfer between the metal centers.Il From the spectral and redox properties of the dimeric complexes, it is apparent that metal-metal interactions can occur, apparently through the T systems of the bridging ligands, even over considerable distances.…”

mentioning

confidence: 99%

Effects of weak metal-metal interactions in ligand-bridged complexes of ruthenium. Dimeric complexes containing ruthenium ions in different coordination environments

Callahan¹,

Brown²,

Meyer³

1975

Inorg. Chem.

124

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AIC405 5 5HThe preparation and characterization of the salts [(NH3)sRu(L)RuCl(bipy)z](PF6)3 (L = pyrazine (pyz), 4,4'-bipyridine (4,4'-bipy), trans-1,2-bis(4-pyridyl)ethylene (BPE), and 1,2-bis(4-pyridyl)ethane (BPA)) are described. The 3+ dimeric ions undergo a reversible one-electron oxidation either chemically or electrochemically in acetonitrile giving the mixed-valence (Ru(II1)-Ru(I1)) ions, [(NH3)5Ru(L)RuCl(bipy)z]J+. In the mixed-valence ions, the site of oxidation is largely localized on the (NH3)5Rugroup. The twice-oxidized 5+ ions have also been shown to exist in solution using electrochemical methods. For the ions where the bridging ligand has an intact n= system (pyz, 4,4'-bipy, or BPE), the effects of weak metal-metal interactions are observed in spectral and reduction potential data and in the appearance of intervalence transfer bands for the mixed-valence ions. With BPA as the bridging ligand, the N-heterocyclic T systems are separated by the saturated -CH2-CH2-linkage, and no evidence for metal-metal electronic interactions has been obtained. From the properties of the intervalence transfer band for the mixed-valence pyrazine-bridged dimer, it can be estimated that electronic interactions in the ground state are lower by a factor of 3 than for the Creutz and Taube ion, [(NH3)5Ru(pyz)Ru(NH3)5]5+.

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The electronic structure of μ-pyrazinedecaamminediruthenium(5+) p-toluenesulfonate

Cited by 28 publications

References 6 publications

Magnetic and spectroscopic properties of FeIIFeIII2(CH3CO2)6L3, L = water or pyridine. Direct observation of the thermal barrier to electron transfer in a mixed-valance complex

Magnetic and spectroscopic properties of FeIIFeIII2(CH3CO2)6L3, L = water or pyridine. Direct observation of the thermal barrier to electron transfer in a mixed-valance complex

Experimental evidence for trapped valences in the mixed-valence complex .mu.-pyrazine-bis(pentaammineruthenium) tosylate. Electron paramagnetic resonance, magnetic susceptibility, and nuclear magnetic resonance results

Effects of weak metal-metal interactions in ligand-bridged complexes of ruthenium. Dimeric complexes containing ruthenium ions in different coordination environments

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