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- ItemMulti-nuclear, high-pressure, operando FlowNMR spectroscopic study of Rh/PPh3 – catalysed hydroformylation of 1-hexene(Cambridge [u.a.] : Soc., 2021) Bara-Estaún, Alejandro; Lyall, Catherine L.; Lowe, John P.; Pringle, Paul G.; Kamer, Paul C. J.; Franke, Robert; Hintermair, UlrichThe hydroformylation of 1-hexene with 12 bar of 1 : 1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well as chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to ensure true operando conditions without gas limitation. 31P{1H} and selective excitation 1H pulse sequences have been periodically interleaved with 1H FlowNMR measurements to detect Rh–phosphine intermediates during the catalysis. Stopped-flow experiments in combination with diffusion measurements and 2D heteronuclear correlation experiments showed the known tris-phosphine complex [RhH(CO)(PPh3)3] to generate rapidly exchanging isomers of the bis-phosphine complex [Rh(CO)2(PPh3)2] under CO pressure that directly enter the catalytic cycle. A new mono-phosphine acyl complex has been identified as an in-cycle reaction intermediate.
- ItemHigh-field phase diagram of the heavy-fermion metal YbRh2Si2(Milton Park : Taylor & Francis, 2006) Gegenwart, P.; Tokiwa, Y.; Westerkamp, T.; Weickert, F.; Custers, J.; Ferstl, J.; Krellner, C.; Geibel, C.; Kerschl, P.; Müller, K.-H.; Steglich, F.The tetragonal heavy-fermion (HF) metal YbRh2Si2 (Kondo temperature TK≈ 25 K) exhibits a magnetic field-induced quantum critical point related to the suppression of very weak antiferromagnetic (AF) ordering (TN = 70 mK) at a critical field of Bc = 0.06 T (B⊥ c). To understand the influence of magnetic fields on quantum criticality and the Kondo effect, we study the evolution of various thermodynamic and magnetic properties upon tuning the system by magnetic field. At B > Bc, the AF component of the quantum critical fluctuations becomes suppressed, and FM fluctuations dominate. Their polarization with magnetic field gives rise to a large increase of the magnetization. At B* = 10 T, the Zeeman energy becomes comparable to kB TK, and a steplike decrease of the quasi-particle mass deduced from the specific-heat coefficient indicates the suppression of HF behaviour. The magnetization M(B) shows a pronounced decrease in slope at B* without any signature of metamagnetism. The field dependence of the linear magnetostriction coefficient suggests an increase of the Yb-valency with field, reaching 3+ at high fields. A negative hydrostatic pressure dependence of B* is found, similar to that of the Kondo temperature. We also compare the magnetization behaviour in pulsed fields up to 50 T with that of the isoelectronic HF system YbIr2Si2, which, due to a larger unit-cell volume, has an enhanced TK of about 40 K.