Isomer-selective conversion is a challenging goal in the rational design of Au clusters. Herein, we demonstrate the isomer-selective conversion of Au(SC) (SC = cyclohexanethiolate) into Au(SR)(SC) in high yields by reactions with gold(I) thiolate (AuSR) complexes. Electrospray ionization mass spectrometry indicated that even numbers of AuSR units are inserted into Au(SR)(SC) to generate Au(SR)(SC) through intermediates Au(SR)(SC) or Au(SR)(SC). These results suggest that the number of constituent atoms in surface Au(I)SR oligomers only increases, while the number of electrons in an Au core is maintained. UV-vis analysis revealed the generation of one of two Au(SR)(SC) isomers in the reactions of Au(SC) with AuSR complexes, in contrast to the formation of both isomers by reactions with thiols. When the structures of Au(SR) are compared with those of the Au(SR) isomers, the partial structure in the Au cores is preserved in the isomer-selective conversion with AuSR complexes, regardless of the structures of the thiolate moiety.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.3c01442 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Isomer-Selective Conversion of Au Clusters by Au(I) Thiolate Insertion.
Inorg Chem
July 2023
Graduate School of Science, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
Isomer-selective conversion is a challenging goal in the rational design of Au clusters. Herein, we demonstrate the isomer-selective conversion of Au(SC) (SC = cyclohexanethiolate) into Au(SR)(SC) in high yields by reactions with gold(I) thiolate (AuSR) complexes. Electrospray ionization mass spectrometry indicated that even numbers of AuSR units are inserted into Au(SR)(SC) to generate Au(SR)(SC) through intermediates Au(SR)(SC) or Au(SR)(SC).
View Article and Find Full Text PDFElucidation of radical- and oxygenate-driven paths in zeolite-catalysed conversion of methanol and methyl chloride to hydrocarbons.
Nat Catal
June 2022
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland.
Understanding hydrocarbon generation in the zeolite-catalysed conversions of methanol and methyl chloride requires advanced spectroscopic approaches to distinguish the complex mechanisms governing C-C bond formation, chain growth and the deposition of carbonaceous species. Here operando photoelectron photoion coincidence (PEPICO) spectroscopy enables the isomer-selective identification of pathways to hydrocarbons of up to C in size, providing direct experimental evidence of methyl radicals in both reactions and ketene in the methanol-to-hydrocarbons reaction. Both routes converge to C molecules that transform into aromatics.
View Article and Find Full Text PDFUnderstanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis.
Nat Commun
June 2017
Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, HCI E 127, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland.
Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively.
View Article and Find Full Text PDFResonance ionization laser ion sources for on-line isotope separators (invited).
Rev Sci Instrum
February 2014
EN Department, CERN, 1211 Geneva, Switzerland.
A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states.
View Article and Find Full Text PDFElectrochemical conversion of unreactive pyrene to highly redox-active 1,2-quinone derivatives on a carbon nanotube-modified gold electrode surface and its selective hydrogen peroxide sensing.
Langmuir
August 2013
Environmental and Analytical Chemistry Division, School of Advanced Sciences, Vellore Institute of Technology University, Vellore-632 014, India.
Pyrene (PYR) is a rigid, carcinogenic, unreactive, and nonelectrooxidizable compound. A multiwalled carbon nanotube (MWCNT)-modified gold electrode surface-bound electrochemical oxidation of PYR to a highly redox-active surface-confined quinone derivative (PYRO) at an applied potential of 1 V versus Ag/AgCl in pH 7 phosphate buffer solution has been demonstrated in this work. Among various carbon nanomaterials examined, the pristine MWCNT-modified gold electrode showed effective electrochemical oxidation of the PYR.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!