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91.
Dr. Bidyut B. Sarma Jonglack Kim Jonas Amsler Dr. Giovanni Agostini Dr. Claudia Weidenthaler Norbert Pfänder Dr. Raul Arenal Dr. Patricia Concepción Dr. Philipp Plessow Prof. Dr. Felix Studt Dr. Gonzalo Prieto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5855-5864
Realizing the full potential of oxide-supported single-atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one-pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization-hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double-bond migration and anti-Markovnikov α-olefin hydrosilylation, respectively. First-principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single-pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio-selectivity (>95 %) even from industrially-relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide-supported single-atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
92.
Michael Ruppel Dr. Dominik Lungerich Sabrina Sturm Dr. Rainer Lippert Dr. Frank Hampel Prof. Dr. Norbert Jux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3287-3296
Tetraaryltetrabenzoporphyrins (TATBPs) show, due to their optoelectronic properties, rising potential as dyes in various fields of physical and biomedical sciences. However, unlike in the case of porphyrins, the potential structural diversity of TATBPs has been explored only to little extent, owed mainly to synthetic hurdles. Herein, we prepared a comprehensive library of 30 TATBPs and investigated their fundamental properties. We elucidated structural properties by X-ray crystallography and found explanations for physical properties such as solubility. Fundamental electronic aspects were studied by optical spectroscopy as well as by electrochemistry and brought in context to the stability of the molecules. Finally, we were able to develop a universal synthetic protocol, utilizing a readily established isoindole synthon, which gives TATBPs in high yields, regardless of the nature of the used arylaldehyde and without meticulous chromatographic purifications steps. This work serves as point of orientation for scientists, that aim to utilize these molecules in materials, nanotechnological, and biomedical applications. 相似文献
93.
Dr. Jan Schwabedissen Pia C. Trapp Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel Zhuang Wu Xianxu Chu Prof. Dr. Xiaoqing Zeng 《ChemistryOpen》2020,9(9):913-920
Difluorothiophosphoryl isocyanate, F2P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar-matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X-ray diffraction (XRD) in the gas phase and solid state, respectively. The analysis of the spectroscopic data and molecular structures is complemented by extensive quantum-chemical calculations. Theoretically, the Cs symmetric syn-conformer is predicted to be the most stable conformation. Rotation about the P−N bond requires about 9 kJ mol−1 and the predicted existence of an anti-conformer is dependent on the quantum-chemical method used. This syn-orientation of the isocyanate group is the only one found in the gas phase and contained likewise in the crystal. The overall molecular structure is very similar in gas and solid, despite in the solid state the molecules arrange through intramolecular O⋅⋅⋅F contacts into layers, which are further interconnected by S⋅⋅⋅N, S⋅⋅⋅C and C⋅⋅⋅F contacts. Additionally, the photodecomposition of F2P(S)NCO to form CO, F2P(S)N, and F2PNCO is observed in the solid Ar-matrix. 相似文献
94.
Bidyut B. Sarma Jonglack Kim Jonas Amsler Giovanni Agostini Claudia Weidenthaler Norbert Pfnder Raul Arenal Patricia Concepcin Philipp Plessow Felix Studt Gonzalo Prieto 《Angewandte Chemie (International ed. in English)》2020,59(14):5806-5815
Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
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Based on the Michael reaction of multifunctional acetoacetates with multiacrylates, in the presence or absence of dimethacrylates, tailor made matrix materials can be prepared. This can be achieved in a one- or two-step process. The Michael addition (first step) can be followed by radiation curing of excessive acrylate (second step). 相似文献
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