New one-step methods for the synthesis of the metallonium dication [Ru(η5-C5Me5)(η5:σ:σ-C5Me3(CH2)2]2+ and its heteroannular analog starting from decamethylruthenoceneand its heteroannular analog starting from decamethylruthenocene

Kamyshova, A. A.; Kreindlin, A. Z.; Rybinskaya, M. I.; Petrovskii, P. V.

doi:10.1007/bf02494787

“…Al arge body of work hase manated from the A. N. Nesmeyanov Instituteo fO rganoelement Compounds (Moscow,R ussian Federation)o ver the past 30 years on the organometallic chemistry of metallocenes, especially decamethylmetallocenes, [50][51][52][53][54][55][56][57] including the UV photolysis of [Cp* 2 Ru II ]i ns trong acidic solutions. [58,59] The main focus of thesep reviouss tudies was the synthesis and characterization of cationic derivatives of [Cp* 2 Ru II ], especially with regard to the stabilization of up to three carbocationic sites (CH 2 + )o nt he cyclopentadienyl rings by as ingle ruthenium metal atom [54,55] and the reactivity of these cations towards strong nucleophiles. [56,57] The proposed mechanism was divided into three steps:R u IV hydride formation in the dark [Eq.…”

Section: Photogeneration Of H 2 Fromacidified Dce By Using [Cp 2 *Ru mentioning

confidence: 99%

Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Rivier

¹

,

Peljo

²

,

Maye

³

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp* 2 Ru II ]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additionals ensitizer.E lectrochemical, gas chromatographic, and spectroscopic (UV/Vis, 1 Ha nd 13 CNMR) measurements corroborated by DFTc alculations indicated that the production of hydrogen occurs by at wo-stepp rocess. First, decamethylruthenocene hydride [Cp* 2 Ru IV (H)] + is formed in the presence of an organic acid. Subsequently, [Cp* 2 Ru IV (H)] + is reversibly reduced in ah eterolytic reaction with one-photon excitation leadingt oafirst releaseo fh y-drogen. Thereafter,t he resultant decamethylruthenocenium ion [Cp* 2 Ru III ] + is further reduced with as econd releaseo f hydrogenb yd eprotonation of am ethyl group of [Cp* 2 Ru III ] + .E xperimental and computational data show spontaneous conversion of [Cp* 2 Ru II ]t o[ Cp* 2 Ru IV (H)] + in the presence of protons. Calculations highlight that the first reductioni se ndergonic (DG 0 = 108 kJ mol À1 )a nd needs an input of energy by light for the reactiont oo ccur.T he hydricityo ft he methylp rotons of [Cp* 2 Ru II ]w as also considered.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

show abstract

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling

Rivier

¹

,

Peljo

²

,

Vannay

³

et al. 2017

View full text Add to dashboard Cite

The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene,C p 2 *Ru II (Cp* = C 5 Me 5 ), is reported. The use of am etallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer.T he mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 HNMR) measurements.T he photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on af luorinated tin oxide electrode surface.Apromising internal quantum yield of 25 %w as obtained. Optimal experimental conditionsespecially the use of weakly coordinating solvent and counterions-are discussed.Thedevelopmentofsimpleandefficientmethodstoproduce molecular hydrogen (H 2 )i st he focus of intense research. Va rious state-of-the-art multicomponent artificial photosystems for H 2 generation are currently under heavy scrutiny and generally consist of ah ighly engineered catalyst, photosensitizer,electron mediator or relay combinations, [1] and are often fueled by sacrificial electron donors (for example, triethylamine, [2] triethanolamine, [2b] benzyl-dihydronicotinamide, [3] and so forth). Thel atter irreversibly oxidizes upon charge transfer and provides protons and electrons to the catalyst. Consequently,s acrificial systems consume af uel to produce H 2 while electrochemical systems only consume electricity (that is now being increasingly produced in as ustainable manner). Indeed, the electrode can both accept and donate electrons.N oi rreversible reactions take place at this step,a nd the protons are supplied from the solution.Metallocenes appear as an attractive class of molecules capable of achieving the complex photogeneration of H 2 by themselves.Indeed, they are able to both reduce protons and undergo photoactivation. Therefore,t hese "all-in-one" molecules would offer an interesting alternative to state-ofthe-art multicomponent photosystems as fewer electron transfer steps are involved. Moreover,they are simple,easily synthesized molecules,w ith ligands and metal centers that may be tuned to obtain certain desired properties,s uch as tailored solubility,a bsorbance wavelength, or redox potentials.Recently,w ed emonstrated the possibility to produce H 2 in the dark using decamethylferrocene (Cp 2 *Fe II ;C p* = C 5 Me 5 )asanelectron donor in abiphasic system.[4] Motivated by these early findings,weset out to explore the reactivity of other metallocenes as suitable electron donors.I nterestingly, both osmocene (Cp 2 Os II ;C p = C 5 H 5 ) [5] and decamethylosmocene (Cp 2 *Os II ) [6] demonstrated the capability to produce H 2 upon light irradiation. Other works have proposed the use of asingle molecule to achieve photogeneration of H 2 . Fore xample,C ole-Hamilton [7] reported ap latinum phosphine compound, while both Miller [8] and Gray [9] used iridium chloride complexes.Herein, we report Cp 2 *Ru II as the first metallocene capable of perfo...

show abstract

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling

Rivier

¹

,

Peljo

²

,

Vannay

³

et al. 2017

View full text Add to dashboard Cite

The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene,C p 2 *Ru II (Cp* = C 5 Me 5 ), is reported. The use of am etallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer.T he mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 HNMR) measurements.T he photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on af luorinated tin oxide electrode surface.Apromising internal quantum yield of 25 %w as obtained. Optimal experimental conditionsespecially the use of weakly coordinating solvent and counterions-are discussed.Thedevelopmentofsimpleandefficientmethodstoproduce molecular hydrogen (H 2 )i st he focus of intense research. Va rious state-of-the-art multicomponent artificial photosystems for H 2 generation are currently under heavy scrutiny and generally consist of ah ighly engineered catalyst, photosensitizer,electron mediator or relay combinations, [1] and are often fueled by sacrificial electron donors (for example, triethylamine, [2] triethanolamine, [2b] benzyl-dihydronicotinamide, [3] and so forth). Thel atter irreversibly oxidizes upon charge transfer and provides protons and electrons to the catalyst. Consequently,s acrificial systems consume af uel to produce H 2 while electrochemical systems only consume electricity (that is now being increasingly produced in as ustainable manner). Indeed, the electrode can both accept and donate electrons.N oi rreversible reactions take place at this step,a nd the protons are supplied from the solution.Metallocenes appear as an attractive class of molecules capable of achieving the complex photogeneration of H 2 by themselves.Indeed, they are able to both reduce protons and undergo photoactivation. Therefore,t hese "all-in-one" molecules would offer an interesting alternative to state-ofthe-art multicomponent photosystems as fewer electron transfer steps are involved. Moreover,they are simple,easily synthesized molecules,w ith ligands and metal centers that may be tuned to obtain certain desired properties,s uch as tailored solubility,a bsorbance wavelength, or redox potentials.Recently,w ed emonstrated the possibility to produce H 2 in the dark using decamethylferrocene (Cp 2 *Fe II ;C p* = C 5 Me 5 )asanelectron donor in abiphasic system.[4] Motivated by these early findings,weset out to explore the reactivity of other metallocenes as suitable electron donors.I nterestingly, both osmocene (Cp 2 Os II ;C p = C 5 H 5 ) [5] and decamethylosmocene (Cp 2 *Os II ) [6] demonstrated the capability to produce H 2 upon light irradiation. Other works have proposed the use of asingle molecule to achieve photogeneration of H 2 . Fore xample,C ole-Hamilton [7] reported ap latinum phosphine compound, while both Miller [8] and Gray [9] used iridium chloride complexes.Herein, we report Cp 2 *Ru II as the first metallocene capable of perfo...

show abstract

New one-step methods for the synthesis of the metallonium dication [Ru(η5-C5Me5)(η5:σ:σ-C5Me3(CH2)2]2+ and its heteroannular analog starting from decamethylruthenoceneand its heteroannular analog starting from decamethylruthenocene

Cited by 4 publications

References 9 publications

Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling

Contact Info

Product

Resources

About