Nitrosyl Ruthenium Diolato Complexes

Barth, Michael; Kästele, Xaver; Klüfers, Peter

doi:10.1002/ejic.200300925

Cited by 11 publications

(8 citation statements)

References 7 publications

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“…Two oxidation waves were observed, separated by about 0.6 V which would be typical for an o-quinone/o-semiquinone/ catecholate redox series. [13][14][15] Reduction at rather negative potentials was observed to occur irreversibly except for the system 2 0/À with the acceptor substituted Q 2À (tcc 2À ) and the less electron rich Ru. In general, the redox potentials reflect the donor/acceptor difference of Q (dtbc vs. tcc) and the metal (Ru ligand.…”

Section: Resultsmentioning

confidence: 97%

“…[7,8] A preferable approach to such an analysis is the combination of spectroelectrochemical methods using IR and UV-vis-NIR spectroscopy or EPR (for paramagnetic states). [9] Combining two classical noninnocently behaving ligands, the biochemically relevant [1,10,11] NO (NO + , NO * , NO À ) [12] and oquinone/catecholate redox series (Q, Q * À , Q 2À ), [13][14][15] with the organometallic complex fragment [M(Cp*)] + = [M(C 5 Me 5 )] + , M = Ru or Os (M 2 + , M 3 + , M 4 + ), we describe such an analysis in the following, using electron-rich 3,5-di-tert-butylcatecholate (dtbc) and electron-deficient 3,4,5,6-tetrachlorocatecholate (tcc). Some [Ru (Cp*)-catecholate(NO)] compounds have been described before.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones

Scherer

Hartenbach

Lissner

et al. 2021

Zeitschrift anorg allge chemie

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Neutral complexes [M II (C 5 Me 5 )(Q 2À )(NO + )] with M = Ru or Os and the catecholates Q 2À with 3,5-di-tert-butyl (dtbc) or 3,4,5,6tetrachloro substituents (tcc) were identified with the oxidation and charge states indicated. Reversible electron transfer was analyzed spectroelectrochemically (EPR, UV-vis-NIR, IR), supported by DFT calculations. Reversible reduction was observed for [Ru(C 5 Me 5 )(tcc)(NO)] to occur on the nitrosyl ligand to yield the NO radical complex [Ru II (C 5 Me 5 )(tcc 2À )(NO * )] À , whereas the stepwise oxidation yielded o-semiquinone cations, [M II-(C 5 Me 5 )(Q * À )(NO + )] + , and dications. The metals remained in the stable low-spin d 6 states, Ru II and Os II , respectively. Redox potentials were found to depend strongly on the donor or acceptor substitution pattern at Q n .

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones

Scherer

Hartenbach

Lissner

et al. 2021

Zeitschrift anorg allge chemie

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“…Accordingly, in the presence of dimethylamine borane as a reducing agent, Ru(acac) 3 is reduced to a ruthenium(II) species, which is most likely in the form of mer-[Ru(N 2 Me 4 ) 3 (acac)H]. The mer-form of the complex is also anticipated to be favorable over the fac-form because of less competition between the O- and N-donor ligand [38,39]. …”

Section: Resultsmentioning

confidence: 99%

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III) Acetylacetonate

2015

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The catalytic activity of ruthenium(III) acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II) species is formed in situ from the reduction of ruthenium(III) and characterized using UV-Visible, Fourier transform infrared (FTIR), 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II) species is mer-[Ru(N2Me4)3(acac)H]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac)3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II) catalyst formed from the reduction of ruthenium(III) acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

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“…The total structure factors, S(Q) (Fig. 10a were assigned according to the structural data for related ruthenium complexes 23,25 and RuO 2 . 10).…”

Section: Effects Of Amine Structurementioning

confidence: 99%

“…The peaks indicated by arrows in Fig. 10a were assigned according to the structural data for related ruthenium complexes 23,25 and RuO 2 . 26 Peak 1 arises from the C-C Fig.…”

Section: Effects Of Amine Structurementioning

confidence: 99%

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

Murakami

Hirose

et al. 2015

J. Mater. Chem. C

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Highly conductive ruthenium metal (Ru 0 ) thin films and ruthenium oxide (RuO 2 ) films were prepared by a solution process. Solutions prepared from ruthenium(III) nitrosyl acetate and amines were spin-coated, and Ru 0 and RuO 2 thin films were formed after annealing in an inert atmosphere (nitrogen or vacuum) and oxygen, respectively. It was observed that amine-coordinated oxo-ruthenium clusters were formed in the precursor solution. The coordinated amines resulted in a change from oxidative decomposition to reductive decomposition of the ruthenium precursor under inert atmospheric conditions. The effects of different amine structures were compared, and alkanolamine and amino acids were found to produce Ru 0 films of higher quality (lower resistivity and higher surface flatness) than alkyl amines with primary amines being preferred to secondary and tertiary ones. These results were correlated with the structures of ruthenium complexes revealed by methods including high-energy X-ray diffraction with total correlation function and pair distribution function analyses. The resistivity values of Ru 0 and RuO 2 thin films prepared from ruthenium-alkanolamine complexes were 2.1 Â 10 À5 and 4.3 Â 10 À4 O cm, respectively, similar to those of vacuum-processed Ru 0 and RuO 2 ones. The Ru 0 film showed high stability against oxidation during further annealing in oxygen, even at nanometer-thickness (e.g., 25 nm).Technology (JAIST),

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Nitrosyl Ruthenium Diolato Complexes

Abstract: [mer-(dien)(NO)Ru(AnErytH -2 )]BPh 4 ·2 H 2 O (1), [mer-(dien)

Cited by 11 publications

References 7 publications

Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones

Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III) Acetylacetonate

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

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Nitrosyl Ruthenium Diolato Complexes

Abstract: [mer-(dien)(NO)Ru(AnErytH -2 )]BPh 4 ·2 H 2 O (1), [mer-(dien)

Cited by 11 publications

References 7 publications

Analysis of Multiple Redox Sites in Complexes [M(C5Me5)(Q)(NO)]n, M=Ru or Os, Q=o‐Quinones

Analysis of Multiple Redox Sites in Complexes [M(C5Me5)(Q)(NO)]n, M=Ru or Os, Q=o‐Quinones

A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III) Acetylacetonate

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

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Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones

Analysis of Multiple Redox Sites in Complexes [M(C₅Me₅)(Q)(NO)]ⁿ, M=Ru or Os, Q=o‐Quinones