Spin trapping and some reactions of ruthenium-centred radicals

Sostero, Silvana; Rehorek, Detlef; Polo, Eleonora; Traverso, O.

doi:10.1016/s0020-1693(00)85138-5

Cited by 23 publications

(21 citation statements)

References 20 publications

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“…Contrary to the previous reports [34,52,69], in recent studies no photochemical dissociation of the terminal CO ligand was identified. Instead the cleavage of Ru-CO bridged and Ru-Ru bonds was recognized to follow the excitations at 265 and 330 nm of II-b and II-nb, respectively (paths a and b in Scheme 1) [3,68,69].…”

contrasting

confidence: 83%

“…Instead the cleavage of Ru-CO bridged and Ru-Ru bonds was recognized to follow the excitations at 265 and 330 nm of II-b and II-nb, respectively (paths a and b in Scheme 1) [3,68,69]. In the former case, the monobridged dimeric radical species is formed, whereas in the latter the monomeric [CpRu(CO) 2 ] · radicals are generated photochemically.…”

mentioning

confidence: 99%

“…toluene, carbon tetrachloride) all photochemically generated radicals are transformed into the monomeric Ru(II) complexes, e.g. [CpRu(CO) 2 Cl] [3,34,68,69]. In the presence of the ligating solvents (e.g.…”

mentioning

confidence: 99%

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Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

Jaworska

Macyk

Stasicka

2004

Structure and Bonding

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The structures of all possible isomeric forms of the [M(h 5 -C 5 H 5 )(CO) 2 ] 2 complexes (M=Fe, Ru) are calculated with the use of the DFT method. The results indicate that both dimers can occur in three stable forms: bridged trans and cis and non-bridged trans. Contrary to the previous reports, the cis non-bridged form turns out to be an unstable transition state. Instead, an additional stable structure, a gauche non-bridged one, is found but only in the case of the Ru compound. Without any outer-sphere interaction the trans-bridged form is of the lowest energy for both dimers. The results are compared with the experimental data. Strong impact of the medium on the stability of the individual structures in solution is emphasized. The electronic spectra of all stable forms, calculated using TDDFT method, reproduce well spectral properties of both complexes. Moreover, they are useful in interpreting the medium effect and photochemical behaviour. The photoreactivity is briefly reviewed pointing at analogies and differences between the Fe and Ru complexes.

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contrasting

confidence: 83%

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confidence: 99%

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Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

Jaworska

Macyk

Stasicka

2004

Structure and Bonding

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“…The natural isotopes 99Ru and l°tRu (both I= 5/2) can give rise to different hyperfine coupling constants provided that the difference in aRu between these two isotopes is larger than the line width. This was the case for the radicals [RuCp(CO)2] ÷" [36] and [Ru(LXPPh3)(CO)2(o-O2C6C14)] n+ [35] but not for the radicals under study.…”

Section: Esr Spectramentioning

confidence: 85%

“…Thus, the semiquinone radicals [Ru(L)(PPh3)(CO)2(o-O2C6C14)] n+ [L=PPh 3 (n = 1), halide (n =0)] [35] could be observed as persistent radicals, whereas the metal-centred radicals [RuCp(CO)2] +" [36] and [Ru(SiMe3)(CO)4] +" [37] could only be detected by using a spin trap. The natural isotopes 99Ru and l°tRu (both I= 5/2) can give rise to different hyperfine coupling constants provided that the difference in aRu between these two isotopes is larger than the line width.…”

Section: Esr Spectramentioning

confidence: 99%

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

Nieuwenhuis

Loon

Moraal

et al. 1995

Journal of Organometallic Chemistry

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Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The photochemical quantum yield for the disappearance of the ipr-DAB complex was ca. 0.30, but only 0.05 for the iPr-PyCa complex. Low-temperature measurements and flash photolysis data showed that this difference in behaviour is due to the thermal instability of the dimer [Ru(Me)(CO)2(ipr-PyCa)]2, which leads to partial regeneration of the parent complex at room temperature. At temperatures below 163 K, the photodecomposition into radicals was followed by electron transfer, leading to formation of the ions [(CO)sMn]-and [Ru(Me)(SXCO)z(a-diimine)] + in 2-MeTHF and the contact ion-pair [(CO)sMn-... Ru(Me)(CO)z(a-diimine) +] in 2-chlorobutane. Similar photodisproportionation products were formed upon irradiation of thc complexes at room temperature in the presence of N-or P-donor ligands.

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Temperature-Dependent Photophysical, Photochemical and Redox Properties of Novel Complexes (CO)2CpRu–Ru(Ln)–RuCp(CO)2 and (CO)2CpRu–Ru(Ln)–SnPh3 [Ln = (CO)2(N,N′-diisopropyl-1,4-diaza-1,3-butadiene)]

Slageren¹,

Hartl²,

Stufkens³

2000

Eur. J. Inorg. Chem.

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The photophysical, photochemical and redox properties of the title complexes were investigated. Resonance Raman measurements revealed the lowest‐energy electronic transition to possess σ→π* character. At low temperatures, long‐lived near‐IR emission was observed. Irradiation in solution results in homolytic splitting of a Ru–Ru bond as the primary step, followed by secondary reactions of the radical fragments depending on the experimental conditions. (Spectro)electrochemical investigations of the title species proved that the axial [RuCp(CO)2] groups exert a stabilising influence on the corresponding radical cations, while destabilising the corresponding radical anions, compared to the redox behaviour of other ruthenium complexes of this type.

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Spin trapping and some reactions of ruthenium-centred radicals

Cited by 23 publications

References 20 publications

Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

Structure, Spectroscopy and Photochemistry of the [M(η5-C5H5)(CO)2]2 Complexes (M=Fe, Ru)

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

Temperature-Dependent Photophysical, Photochemical and Redox Properties of Novel Complexes (CO)2CpRu–Ru(Ln)–RuCp(CO)2 and (CO)2CpRu–Ru(Ln)–SnPh3 [Ln = (CO)2(N,N′-diisopropyl-1,4-diaza-1,3-butadiene)]

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