Oxidative dehydrogenation of ethylenediamine complexes of ruthenium(II)

Mahoney, Dennis F.; Beattie, James K.

doi:10.1021/ic50129a014

Cited by 56 publications

(34 citation statements)

References 2 publications

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“…[Ru(bpy) 2 L](PF 6 ) 2 (L = en, tn, or bn) was synthesized in a similar manner to a published method 3 for the en complex. The synthesized bn complex was confirmed by elemental analysis 20 and ESI-MS.…”

Section: Methodsmentioning

confidence: 99%

“…2 + to give the diimine complex, 3 while Ollino and Rest reported the photochemical oxidation of [Ru(bpy) 2 …”

Section: (En)]mentioning

confidence: 99%

“…[Ru(bpy) 2 2+ , with the removal of AN appeared at a collision energy of 15% (indicated by LCQ's own way), half of the parent ions dissociated to fragments at an energy of 20%, and all of the parent ions dissociated at 25% and another fragment was not observed. The MS/MS spectrum of [Ru(bpy) 2 …”

Section: (Bn)](pf 6 )mentioning

confidence: 99%

“…[1][2][3][4] These studies have shown that the oxidative dehydrogenation reaction took place first by the oxidation of Ru( ) to Ru( ) to form a 17 electron complex, which was then transformed to a diimine complex via a monoimine intermediate. 3,5,6,7 [Ru(bpy) 2 L] 2 + complexes, where bpy = 2,2 -bipyridine, L = ehtylenediamine (en), 1,3-propanediamine (tn), or 1,4-butanediamine (bn) ( 1 , 2 , 3 in Fig. 1), exhibit strong metalto-ligand charge-transfer (MLCT) absorption peaks at around 450-500 nm in acetonitrile.…”

mentioning

confidence: 99%

“…1), exhibit strong metalto-ligand charge-transfer (MLCT) absorption peaks at around 450-500 nm in acetonitrile. Among them, Meyer and coworkers showed the electrolytic oxidation of [Ru(bpy) 2 …”

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confidence: 99%

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Detection of Ligand-Substitution Intermediates in the Photoreactions of Bis(2,2′-bipyridine)butanediamineruthenium(II) Complex Using Electrospray Ionization Mass Spectrometry

Arakawa¹,

Abe²,

Abura³

et al. 2002

Bulletin of the Chemical Society of Japan

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The photolysis of [Ru(bpy) 2 (bn)] 2 + (bpy = 2,2 -bipyridine, bn = 1,4-butanediamine) in acetonitrile and acetone by light of wavelength longer than 420 nm was studied by electrospray ionization mass spectrometry (ESI-MS). The results were different from those of two other amine complexes, [Ru(bpy) 2 (en)] 2 + and [Ru(bpy) 2 (tn)] 2 + (en = ethylenediamine and tn = 1,3-propanediamine). An analysis of the irradiation time course revealed that one end of the bn ligand is quickly dissociated to form a solvent-coordinated complex, [Ru(bpy) 2 (bn)(AN)] 2 + (AN = acetonitrile), and its protonated complex, [Ru(bpy) 2 (bn + H)(AN)] 3 + . These solvent-coordinated complexes were not observed in the photochemical reactions of the en or tn complex. The difference in photolysis is due to the fact that the coordination of the bn ligand in [Ru(bpy) 2 (bn)] 2 + is less stable than the en or tn ligand. Both the en and tn complexes formed oxygenated complexes, while the bn complex did not form such a complex. This can be explained by the incorporation of singlet oxygen during the photochemical reaction.Several dehydrogenation reactions of aliphatic amines, such as ethylenediamine chelating to Ru( ) complex, have been studied by chemical oxidation or electrochemical oxidation reactions.1-4 These studies have shown that the oxidative dehydrogenation reaction took place first by the oxidation of Ru( ) to Ru( ) to form a 17 electron complex, which was then transformed to a diimine complex via a monoimine intermediate. 3,5,6,7 [Ru(bpy) 2 L] 2 + complexes, where bpy = 2,2 -bipyridine, L = ehtylenediamine (en), 1,3-propanediamine (tn), or 1,4-butanediamine (bn) ( 1 , 2 , 3 in Fig. 1 8 Although the oxidative dehydrogenation reactions were believed to occur by MLCT excitation, 9 their expected reaction intermediates, the Ru( ) complex and the monoimine complex, were too unstable to be isolated or identified; therefore, the reaction pathway to the diimine complex remains unclear.Electrospray ionization mass spectrometry (ESI-MS), developed by Fenn and coworkers, 10-12 has become a powerful technique for the detection and identification of reaction products and their intermediates. [13][14][15][16][17] We previously studied the ESI-MS analysis on the photochemical reaction of [Ru(bpy) 2 -(en)] 2 + in acetonitrile. By using an isotope-labeled complex, we were able to confirm that the complex was transformed to the diimine complex via a monoimine intermediate. In addition, we detected a new oxygenated complex, which was shown to be a nitroso-complex from an with a solvent. The reaction is considered to proceed via the one-electron oxidation of the Ru( ) complex to a Ru( ) complex and the intermediate with dissociation of one end of the diamine. However, such reaction intermediates for the ligand substitution process have not been detected for the aliphatic amine complexes. In addition, the reaction pathway to form Fig. 1.Structures of bis(2,2 -bipyridine)diamineruthenium( ) complexes.

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Section: Methodsmentioning

confidence: 99%

“…2 + to give the diimine complex, 3 while Ollino and Rest reported the photochemical oxidation of [Ru(bpy) 2 …”

Section: (En)]mentioning

confidence: 99%

Section: (Bn)](pf 6 )mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Detection of Ligand-Substitution Intermediates in the Photoreactions of Bis(2,2′-bipyridine)butanediamineruthenium(II) Complex Using Electrospray Ionization Mass Spectrometry

Arakawa¹,

Abe²,

Abura³

et al. 2002

Bulletin of the Chemical Society of Japan

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Platinum‐Group Metals, Compounds

Giandomenico

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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The platinum‐group metals, ruthenium, osmium, rhodium, iridium, palladium, and platinum, form binary compounds, coordination complexes, and organometallic compounds. Compounds of each of these metals, which exhibit a range of oxidation states, are summarized. Some of the more useful starting materials are noted, as are the most important uses for the compounds of each individual element. There are catalytic applications for the compounds of all six metals; chemotherapeutic applications for platinum compounds; oxidations by ruthenium and osmium compounds; plating and coating uses for platinum and palladium compounds; metal anode applications for iridium and rhodium compounds; and biological applications of ruthenium compounds. The economic aspects of the platinum‐group metal compounds are summarized, as are the most significant health and safety concerns of working with these compounds.

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