Ruthenium 6 2+, photolysis

To substitute the strongly bound axial CO ligand of the ruthenium or osmium center, it is necessary to employ more drastic conditions than simple stirring at room temperature. Imamura (11,20) used photolysis to synthesize porphyrin trimers on the basis of simultaneous coordination of two 4-pyridyl porphyrins to the same ruthenium porphyrin (12, Fig. 3). Some interesting photophysical behavior was observed for these systems. The trimers have an extra UV-Vis absorption band at about 450 nm which is ascribed to metal-ligand charge transfer (MLCT), a d7r(Ru(II))-7r (OEP) transition. This band shows a batho-chromic shift in more polar solvents, and decreased in intensity when... 

Barrau and coworkers have synthesized a series of iron and ruthenium complexes by irradiation of Me2HGe(CH)KGeMe2H and Me2HGe(CH)K SiMe2H (n = 1, 2) in the presence of Fe(CO)5 and Ru3(CO)i293. In each case irradiation causes CO loss, with the formation of the M(CO)4 species (reaction 43). When n = 2 the products are photostable with n = 1 (65) a mixture of products (66-69) are obtained due to secondary photolysis (reaction 44). The mechanism, outlined in Scheme 23, is presented to explain these observations. 

Ru(edta)(H20)] reacts very rapidly with nitric oxide (171). Reaction is much more rapid at pH 5 than at low and high pHs. The pH/rate profile for this reaction is very similar to those established earlier for reaction of this ruthenium(III) complex with azide and with dimethylthiourea. Such behavior may be interpreted in terms of the protonation equilibria between [Ru(edtaH)(H20)], [Ru(edta)(H20)], and [Ru(edta)(OH)]2- the [Ru(edta)(H20)] species is always the most reactive. The apparent relative slowness of the reaction of [Ru(edta)(H20)] with nitric oxide in acetate buffer is attributable to rapid formation of less reactive [Ru(edta)(OAc)] [Ru(edta)(H20)] also reacts relatively slowly with nitrite. Laser flash photolysis studies of [Ru(edta)(NO)]-show a complicated kinetic pattern, from which it is possible to extract activation parameters both for dissociation of this complex and for its formation from [Ru(edta)(H20)] . Values of AS = —76 J K-1 mol-1 and A V = —12.8 cm3 mol-1 for the latter are compatible with AS values between —76 and —107 J K-1mol-1 and AV values between —7 and —12 cm3 mol-1 for other complex-formation reactions of [Ru(edta) (H20)]- (168) and with an associative mechanism. In contrast, activation parameters for dissociation of [Ru(edta)(NO)] (AS = —4JK-1mol-1 A V = +10 cm3 mol-1) suggest a dissociative interchange mechanism (172). 

The systems that we investigated in collaboration with others involved intermolecular and intramolecular electron-transfer reactions between ruthenium complexes and cytochrome c. We also studied a series of intermolecular reactions between chelated cobalt complexes and cytochrome c. A variety of high-pressure experimental techniques, including stopped-flow, flash-photolysis, pulse-radiolysis, and voltammetry, were employed in these investigations. As the following presentation shows, a remarkably good agreement was found between the volume data obtained with the aid of these different techniques, which clearly demonstrates the complementarity of these methods for the study of electron-transfer processes. 

Janetka and Rich (78) have utilized the considerable stability of ruthenium-77-arene systems in the synthesis of cyclic tripeptides as analogs of the protease inhibitor K-13 (cf. 34, Scheme 28). Their approach involves the construction of linear tripeptide complexes (35) using diimide/HOBt coupling of [Ru(Cp)(Boc-p-Cl-PheOH)]PF6 (Cp = 775-C5H5) with the appropriate dipeptide ester. Cyclization of 35 affords the biphenyl ether 36, which on photolysis (350 nm) gives 34. 

A synthesis of much relevance is that of the copolymer (4-methyl, 4 -vinyl 2,2 bipyridine/styrene)-pendant tris(2,2 -bipyridyl) ruthenium(II) complex as sensitizer for water photolysis with solar irradiation [19]. 

The photochemical studies of transition metal hydride complexes that have appeared in the chemical literature are reviewed, with primary emphasis on studies of iridium and ruthenium that were conducted by our research group. The photochemistry of the molybdenum hydride complexes Mo(tj5-C5H5)2M2] and [MoH4(dppe)2] (dppe = Ph2PCH2CH2PPh2), which eliminate H2 upon photolysis, is discussed in detail. The photoinduced elimination of molecular hydrogen from di-and polyhydride complexes of the transition elements is proposed to be a general reaction pathway. 

Research based on time-resolved XAS in an optical pump-x-ray probe scheme has first been implemented at synchrotron radiation sources. Mills et al. [2] used a 20 Hz repetition rate Nd YAG laser to photolyse carbonmonomyoglobin (MbCO) and monitor the photolysis product with time-resolved XAS around the K-edge of the iron atom. Other studies were carried out on different types of photolyzed systems in liquids, by Thiel et al. [3], Clozza et al. [4], Chance et al. [5,6] and Chen et al. [7,8,9]. All these studies were limited to the nanosecond or longer time domain. We recently reported on time-resolved XANES studies of a Ruthenium complex in water solution reaching the picosecond time scale [10]. This work allows us to evaluate the feasibility of future time-resolved XAS experiments, which we present below together with our new results. 

Intramolecular electron transfer from Ru(II) to Fe(III) in (NH3)3Ru(II) (His-33)cyt(Fe(III)) induced by pulse-radiolysis reduction of Ru(III) in the (NH3)5Ru(III) (His-33)cyt(Fe(III)) complex were investigated [84]. The results obtained differ from those of refs. 77-80 where flash photolysis was used to study the similar electron transfer reaction. It was found [84] that, over the temperature range 276-317 K the rate of electron transfer from Ru(II) to Fe(III) is weakly temperature dependent with EA 3.3 kcal mol 1. At 298 K the value of kt = 53 2 s"1. The small differences in the temperature dependence of the electron tunneling rate in ruthenium-modified cytochrome c reported in refs. 77-80 and 84 was explained [84] by the different experimental conditions used in these two studies. 

While the lowest excited state in ruthenium(II) complexes generally involves a MLCT, a d state is nearby (this aspect will be considered later). Hoggard and Porter13 1 studied the photolysis of [Ru(bpy)3](SCN)2 in DMF and ethanol [Ru(bpy)2(NCS)2] was cleanly isolated from ethanol in this fashion. Wallace and Hoggard132,1331 photolyzed several [Ru(bpy)3]2+ salts preparing the di-anated compounds. Jones and Cole-Hamilton have developed a moderate yield (38%) photochemical synthesis of [Ru(bpy)2Cl2] from [Ru(bpy)3]Cl21341 the authors did not consider product stereochemistry. 

Reduction of [Mo(CO)(Bu C=CH)2Cp] + BF4 with KBHBu3(s) at — 78°C in an atmosphere of carbon monoxide yields a complex of a vinyl substituted y-lactone linked tj3 t]2 (220). The allylidene ruthenium complex 64, obtained by photochemical addition of one alkyne molecule to a /x-carbene derivative, is transformed into pentadienylidene complexes 65 and 66 on photolysis with more alkyne substrate. These reactions show clearly the stepwise growth of chains in alkyne oligomerizations at dimetal centers [Eq. (31)] (221). Similar reactions are also known for dinuclear iron (222), molybdenum (223), and tungsten (224) complexes. 

Kaneko, M.,Takabayashi, N., Yamauchi, Y. and Yamada, A. 1984. Water photolysis by means of visible light with a system composed of Prussian blue and the tris (2,2 -biypridine) ruthenium (II) complex. Bull. Chem. Soc. Jpn., 57, 156-161. 

Komozin PN, Kozakova VM, Miroshnichenko IV, Smitsyn NM. An EPR study of the photolysis of nitrosyl compounds of ruthenium. Russ I Inorg Chem 1983 28 1806. 

Lorkovic IM, Miranda K, Lee B, Bernard S, Schoonover J, Ford PC. Flash photolysis studies of the ruthenium(II) porphyrins Ru(P)(NO)(ONO). Multiple pathways involving reactions of intermediates with nitric oxide. J Am Chem Soc 1998 120 11674. 

Photolysis of complex 125 (arene = benzene) in acetonitrile gives a quantitative yield of cyclopentadienyl tris(acetonitrile) ruthenium complex... 

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