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• W2101964918 abstract "Photochemical reactions are reported for the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)] [α-diimine = pyridine-2-carbaldehyde-N-isopropylimine (iPrPyCa), N,N′-diisopropyl-1,4-diaza-1,3-butadiene (iPr0DAB)] upon irradiation into their lowest-energy absorption band. The radicals [Mn(CO)5] and [Ru(Me)(CO)2(α-diimine)] are formed by homolytic splitting of the MnRu bond; the latter radicals have been characterized by ESR spectroscopy. In THF, the [Ru(Me)(CO)2(iPr-DAB)] radicals dimerize to give [Ru(Me)(CO)2(iPr-DAB)]2, and the corresponding radicals from the iPr-PyCa complex gave an unidentified product. Irradiation of a solution of the complexes in CH2Cl2 or CHCl3 afforded [Mn(Cl)(CO)5] and [Ru(Cl)(Me)(CO)2(α-diimine)] but in apolar solvents such as hexane, completely different photoproducts, viz. [(CO)3Mn-μ-(σ(N),σ(N′),ν2(CN),ν2(C′N′)-iPr-DAB)Ru(Me)(CO)2] and [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2] were obtained. The crystal structure of the last complex was determined. 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)5Mn]− and [Ru(Me)(S)(CO)2(α-diimine)]+ in 2-MeTHF and the contact ion-pair [(CO)5Mn−/3. Ru(Me)(CO)2(α-diimine)+] in 2-chlorobutane. Similar photodisproportion products were formed upon irradiation of the complexes at room temperature in the presence of N- or P-donor ligands." @default.
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• W2101964918 date "1995-05-01" @default.
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• W2101964918 title "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]" @default.
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• W2101964918 doi "https://doi.org/10.1016/0022-328x(94)05300-z" @default.
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