Cyclopentadienyl Ruthenium(II) Complexes with Bridging Alkynylphosphine Ligands: Synthesis and Electrochemical Studies

Credico, Barbara Di; Biani, Fabrizia Fabrizi de; Gonsalvi, Luca; Guerri, Annalisa; Ienco, Andrea; Laschi, Franco; Peruzzini, Maurizio; Reginato, Gianna; Rossin, Andrea; Zanello, Piero

doi:10.1002/chem.200901642

Cited by 19 publications

(15 citation statements)

References 69 publications

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“…At 840 cm −1 , the C–H out-of-plane bending typical of the poly(1,4- cis -isoprene) chains is also detectable. Other bands can be attributed to some non-isoprene compounds, such as such as proteins and phospholipids [35], typically contained in the NR:NH groups of amines (3283 cm −1 ), carbonyl groups of esters (1748–1738 cm −1 ), carboxylic acids (1711 cm −1 ), and amides (1630 and 1541 cm −1 ).…”

Section: Resultsmentioning

confidence: 99%

A Green Approach for Preparing High-Loaded Sepiolite/Polymer Biocomposites

et al. 2018

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Global industry is showing a great interest in the field of sustainability owing to the increased attention for ecological safety and utilization of renewable materials. For the scientific community, the challenge lies in the identification of greener synthetic approaches for reducing the environmental impact. In this context, we propose the preparation of novel biocomposites consisting of natural rubber latex (NRL) and sepiolite (Sep) fibers through the latex compounding technique (LCT), an ecofriendly approach where the filler is directly mixed with a stable elastomer colloid. This strategy favors a homogeneous dispersion of hydrophilic Sep fibers in the rubber matrix, allowing the production of high-loaded sepiolite/natural rubber (Sep/NR) without the use of surfactants. The main physicochemical parameters which control Sep aggregation processes in the aqueous medium were comprehensively investigated and a flocculation mechanism was proposed. The uniform Sep distribution in the rubber matrix, characteristic of the proposed LCT, and the percolative filler network improved the mechanical performances of Sep/NR biocomposites in comparison to those of analogous materials prepared by conventional melt-mixing. These outcomes indicate the suitability of the adopted sustainable procedure for the production of high-loaded clay–rubber nanocomposites with remarkable mechanical features.

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Section: Resultsmentioning

confidence: 99%

A Green Approach for Preparing High-Loaded Sepiolite/Polymer Biocomposites

et al. 2018

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“…Cyclic voltammograms were displayed with the concentrations ca. for C 20 CoÀthioP. The addition of Et 3 NHCl (0.1 mM in CH 3 CN) was carried out using a syringe.).…”

Section: Methodsmentioning

confidence: 99%

“…14,15 These complexes are also well known for exhibiting high stability in different kinds of biological media. 18,19 Through incorporation of a triphenylphosphine moiety as an additional donor to enhance the coordination ability of the metal centres (Scheme 1), 20,21 we recently reported the thiosemicarbazone complex, NiÀthioP as an impressive catalyst for hydrogen production in a homogeneous system. 16,17 Since both the proton transformation in the coordination catalysts and the interactions between the hydrogen atoms and the metal ions are the important factors influencing the proton reduction, the transition metal TSCs complexes might be promising candidates for proton reduction, in the case of the redox potential of the species being well controlled.…”

Section: Introductionmentioning

confidence: 99%

Light-driven hydrogen evolution with a nickel thiosemicarbazone redox catalyst featuring Ni⋯H interactions under basic conditions

Liu

et al. 2015

New J. Chem.

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The photocatalytic hydrogen evolution inspired by the highly evolved, finely tuned molecular photosynthetic systems in nature represents an important process in sustainable solar energy conversion for the near future. By incorporating a phosphine donor within a thiosemicarbazone moiety, a new proton reduction catalyst NiÀthioP, featuring NiÁ Á ÁH interactions was synthesized and structurally characterized. Single crystal structure analysis revealed that the C-S, C-N and N-N bond lengths were all within the normal range of the single and double bonds, suggesting the extensive electron delocalization over the ligand skeleton. The presence of NiÁ Á ÁH interactions relative to the amide group coupled with the easy proton migration pathway involving thioamide/thiolate exchange suggested that the thiosemicarbazone complexes could serve as promising candidates for proton reduction. Luminescence titrations exhibited that NiÀthioP served as efficient luminescent quenchers for the photosensitizer Fl, providing the possibilities for the excited state of Fl to activate these catalysts for proton reduction. The direct generation of hydrogen was achieved by carrying out the photolysis of a solution containing fluorescein as the photosensitizer, and triethylamine as the sacrificial and the redox catalysts. NiÀthioP exhibited high activity with a turnover number (TON) of 8000 moles of H 2 per mole of the catalyst after 24 hours and an initial TOF larger than 500 moles of H 2 per catalyst per hour. To further investigate the potential mechanism for proton reduction, calculations were also performed using density functional theory.

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“…The cross-coupling reaction is in general performed between a terminal alkyne 125 and an electrophilic phosphorus reagent in the form of a halophoshine 153 , mostly chlorophosphine, in the presence of a catalyst such as nickel (Ni(acac) 2 ) [244,266–267] or copper (CuI) [268–270] (Scheme 46). The nickel based catalyst was not suitable for the cross-coupling of alkynes containing a sensitive alkoxy or amino functional group.…”

Section: Reviewmentioning

confidence: 99%