Photodissociation of CO from [Ru3(mu3-O)(mu-OOCCH3)6(CO)L2] in acetonitrile, where L = pyridine, 4-cyanopyridine and methanol

Dalton Transactions : an International Journal of Inorganic Chemistry
Daisuke AkashiTasuku Ito

Abstract

Photodissociation of CO from oxo-centered trinuclear ruthenium clusters [Ru3(mu3-O)(mu-OOCCH3)6(CO)L2] (L = pyridine (py): 1; 4-cyanopyridine (cpy): 2; methanol: 3) dissolved in organic solvents has been examined. Upon photolysis (> or = 290 nm, a 450-W Xe lamp), an absorption peak at 585 nm observed for 1 in CH3CN decreases its intensity and a new absorption band appears and grows at 896 nm. This spectral change, presenting isosbestic points, corresponds to photosubstitution of CO in 1 to form [Ru3(mu3-O)(mu-OOCCH3)6(CH3CN)(py)2] 4. Photoexcitation of carbonyl complexes 2 and 3 in CH3CN also affords the corresponding CH3CN-coordinated complexes [Ru3(mu3-O)(mu-OOCCH3)6(CH3CN)(cpy)2] 6 and [Ru3(mu3-O)(mu-OOCCH3)6(CH3CN)3] 7, respectively. The photosubstitution reactions (excitation wavelength, > or = 290 nm) are well described by the first-order kinetics: k = 7.3 x 10(-4) s(-1) for 1, 4.9 x 10(-4) s(-1) for 2 and 5.1 x 10(-4) s(-1) for 3 (298 K). In the presence of a 100-fold excess of py, photolysis of 1 yields a tris(py) complex [Ru3(mu3-O)(mu-OOCCH3)6(py)3] 5 via photochemical loss of CO followed by coordination of py. The overall reaction (photochemical and thermal) is also confirmed by 1H NMR spectroscopy. The dissociative ...Continue Reading

References

Aug 21, 2001·Inorganic Chemistry·D V ScaltritoG J Meyer
Sep 18, 2001·Inorganic Chemistry·A S DelNegroJ R Schoonover
May 30, 2002·Journal of the American Chemical Society·Casey H LonderganClifford P Kubiak

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Citations

Oct 26, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Mariete B MoreiraSofia Nikolaou
Mar 7, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Feng-Rong DaiZhong-Ning Chen
Oct 8, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Feng-Rong DaiZhong-Ning Chen
Jan 13, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Masaaki AbeYoshio Hisaeda

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