Interactions of the (R) Ru-BINAP catalytic complex with an inorganic matrix in stereoselective hydrogenation of methylacetoacetate: kinetic, XPS and DRIFT studies

Klusoň, Petr; Krystyník, Pavel; Dytrych, Pavel; Bartek, Lukas

doi:10.1007/s11144-016-1078-6

Cited by 4 publications

(2 citation statements)

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“…Our hypothesized compounds are also consistent with the observed binding energy of the Ru 3d 5/2 photoelectron peak at 281.64 eV, which is closer to the value observed for Ru(II) and Ru(III) compounds and farther from Ru 0 (279.01 to 280.20 eV) . Note that the Ru 3d 5/2 photoelectron peak is at 281.3 eV for [RuCl( p -cymene)((R)-BINAP)][Cl], 281.5 eV for [(RuCl 2 ( p -cymene)) 2 ], 281.2 eV for [RuCl 2 ( p -cymene)PR 3 ], and [RuCl( p -cymene)(κ 2 - N -sulfonyl-1,2-ethylenediamine)] at 282.0 eV . Of the three possibilities, the dimeric dication is less likely on steric grounds and the coordinatively unsaturated, 16-electron cation [RuCl( p -cymene)P(C 8 H 17 ) 3 ] + would be expected to be stabilized by the interaction with the nearby [Tf 2 N] − anion.…”

Section: Results and Analysissupporting

confidence: 87%

“…First, the complex complex speciation is different within around 6.1−7.8 nm of the gas−liquid interface, and the Ru atom must at least be ligated by the P(C 8 H 17 ) 3 ligand and one Cl − ligand. The 198.4 eV binding energy of the Cl 2p peak supports the conclusion that Cl is bound to Ru because it is closer to the value observed in solid [(RuCl 2 (p-cymene)) 2 ] (198.1 eV) 81 and much larger than the value observed in [C 2 mim][Cl] (197.1 eV). 25 Although the solvation structure of Cl − in [C 2 mim][Tf 2 N] is expected to differ from the solvation structure of Cl − in [C 2 mim][Cl], much of the shift should be the result of short-range interactions between the Cl − anion and the cation of the ionic liquid solvent, which is identical in 20 Second, the enrichment of the observed Ru complex must be much larger than any enrichment of the dissociated Cl − anion in the ∼6.1− 7.8 nm depth probed by the XPS measurement.…”

Section: Results and Analysissupporting

confidence: 75%

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Probing a Ruthenium Coordination Complex at the Ionic Liquid–Vacuum Interface with Reactive-Atom Scattering, X-ray Photoelectron Spectroscopy, and Time-of-Flight Secondary Ion Mass Spectrometry

et al. 2019

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The speciation, conformation, and reactivity of transition metal complexes at the gas−liquid interface are poorly understood, yet the potential is high for observing chemistry unique to this anisotropic interface and leveraging interfacial structure to control the state and environment of the complex. If transition metal complexes can be designed to populate a liquid−vacuum interface preferentially, then it may be possible to explore catalytic behavior by delivering reactants to the interface with a molecular beam and monitoring the scattering dynamics of reaction products to obtain detailed information on the reaction mechanism. In this initial experimental study, we have used reactive-atom scattering with a hyperthermal F-atom probe, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry to explore the interfacial composition and structure of a ∼2 mg/mL solution of [RuCl 2 (p-cymene)P(C 8 H 17 ) 3 ] in perdeuterated 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide (d 11 -[C 2 mim][Tf 2 N]). These data provide strong evidence that a Ru complex is present at the extreme liquid−vacuum interface with a number density that is higher than expected from the bulk concentration (2−3 vs 0.04%). The experimental data also provide information on the chemical nature and environment of the Ru complex that resides at or near the extreme liquid−vacuum interface.

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