scholarly journals Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction

2019 ◽  
Vol 10 (44) ◽  
pp. 10275-10282 ◽  
Author(s):  
Bastian Schluschaß ◽  
Josh Abbenseth ◽  
Serhiy Demeshko ◽  
Markus Finger ◽  
Alicja Franke ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Evolution ◽  
Computational Results ◽  
Reaction Conditions ◽  
Proton Reduction ◽  
Reaction Selectivity ◽  
The Impact

An N2-bridged ditungsten complex is presented that undergoes N2-splitting or hydrogen evolution upon protonation depending on the acid and reaction conditions. Spectroscopic, kinetic and computational results emphasize the impact of hydrogen bonding on the reaction selectivity.

Urea-Catalyzed Functionalization of Unactivated C–H Bonds

2020 ◽  
Author(s):  
Alex L. Bagdasarian ◽  
Stasik Popov ◽  
Benjamin Wigman ◽  
Wenjing Wei ◽  
woojin lee ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Organic Synthesis ◽  
High Energy ◽  
Acid Catalysts ◽  
Potential Utility ◽  
New Paradigm ◽  
Lewis Acid Catalysts ◽  
Reaction Conditions ◽  
Highly Active ◽  
Acidic Nature

Herein we report the 3,5bistrifluoromethylphenyl urea-catalyzed functionalization of unactivated C–H bonds. In this system, the urea catalyst mediates the formation of high-energy vinyl carbocations that undergo facile C–H insertion and Friedel–Crafts reactions. We introduce a new paradigm for these privileged scaffolds where the combination of hydrogen bonding motifs and strong bases affords highly active Lewis acid catalysts capable of ionizing strong C–O bonds. Despite the highly Lewis acidic nature of these catalysts that enables triflate abstraction from sp<sup>2</sup> carbons, these newly found reaction conditions allow for the formation of heterocycles and tolerate highly Lewis basic heteroaromatic substrates. This strategy showcases the potential utility of dicoordinated vinyl carbocations in organic synthesis.<br>

Urea-Catalyzed Functionalization of Unactivated C–H Bonds

2020 ◽  
Author(s):  
Alex L. Bagdasarian ◽  
Stasik Popov ◽  
Benjamin Wigman ◽  
Wenjing Wei ◽  
woojin lee ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Organic Synthesis ◽  
High Energy ◽  
Acid Catalysts ◽  
Potential Utility ◽  
New Paradigm ◽  
Lewis Acid Catalysts ◽  
Reaction Conditions ◽  
Highly Active ◽  
Acidic Nature

Herein we report the 3,5bistrifluoromethylphenyl urea-catalyzed functionalization of unactivated C–H bonds. In this system, the urea catalyst mediates the formation of high-energy vinyl carbocations that undergo facile C–H insertion and Friedel–Crafts reactions. We introduce a new paradigm for these privileged scaffolds where the combination of hydrogen bonding motifs and strong bases affords highly active Lewis acid catalysts capable of ionizing strong C–O bonds. Despite the highly Lewis acidic nature of these catalysts that enables triflate abstraction from sp<sup>2</sup> carbons, these newly found reaction conditions allow for the formation of heterocycles and tolerate highly Lewis basic heteroaromatic substrates. This strategy showcases the potential utility of dicoordinated vinyl carbocations in organic synthesis.<br>

scholarly journals Self-Assembled Bimetallic Aluminum-Salen Catalyst for the Cyclic Carbonates Synthesis

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4097
Author(s):  
Wooyong Seong ◽  
Hyungwoo Hahm ◽  
Seyong Kim ◽  
Jongwoo Park ◽  
Khalil A. Abboud ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Reaction Pathway ◽  
Kinetic Studies ◽  
Cyclic Carbonate ◽  
Reaction Conditions ◽  
Formation Reaction ◽  
X Ray ◽  
Carbonate Formation ◽  
Salen Aluminum

Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.

scholarly journals The influence of physical parameters on the in-situ metal carbonyl complex formation studied with the Fast On-line Reaction Apparatus (FORA)

2021 ◽  
Vol 109 (4) ◽  
pp. 261-281
Author(s):  
Yves Wittwer ◽  
Robert Eichler ◽  
Dominik Herrmann ◽  
Andreas Türler
Keyword(s):  
Gas Flow ◽  
Metal Carbonyl ◽  
Fission Products ◽  
Reaction Chamber ◽  
Single Atom ◽  
Physical Parameters ◽  
Carbonyl Complex ◽  
Reaction Conditions ◽  
On Line ◽  
The Impact

Abstract The Fast On-line Reaction Apparatus (FORA) was used to investigate the influence of various reaction parameters onto the formation and transport of metal carbonyl complexes (MCCs) under single-atom chemistry conditions. FORA is based on a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes. Those are recoiling from the spontaneous fission source into a reaction chamber flushed with a gas-mixture containing CO. Upon contact with CO, fission products form volatile MCCs which are further transported by the gas stream to the detection setup, consisting of a charcoal trap mounted in front of a HPGe γ-detector. Depending on the reaction conditions, MCCs are formed and transported with different efficiencies. Using this setup, the impact of varying physical parameters like gas flow, gas pressure, kinetic energy of fission products upon entering the reaction chamber and temperature of the reaction chamber on the formation and transport yields of MCCs was investigated. Using a setup similar to FORA called Miss Piggy, various gas mixtures of CO with a selection of noble gases, as well as N2 and H2, were investigated with respect to their effect onto MCC formation and transport. Based on this measurements, optimized reaction conditions to maximize the synthesis and transport of MCCs are suggested. Explanations for the observed results supported by simulations are suggested as well.

scholarly journals Small Changes: Using Assessment to Direct Instructional Practices in Large-Enrollment Biochemistry Courses

2017 ◽  
Vol 16 (1) ◽  
pp. ar7 ◽  
Author(s):  
Xiaoying Xu ◽  
Jennifer E. Lewis ◽  
Jennifer Loertscher ◽  
Vicky Minderhout ◽  
Heather L. Tienson
Keyword(s):  
Hydrogen Bonding ◽  
Student Performance ◽  
Bond Energy ◽  
Multiple Choice ◽  
Instructional Interventions ◽  
Student Responses ◽  
Large Classes ◽  
Instructional Effect ◽  
Large Enrollment ◽  
The Impact

Multiple-choice assessments provide a straightforward way for instructors of large classes to collect data related to student understanding of key concepts at the beginning and end of a course. By tracking student performance over time, instructors receive formative feedback about their teaching and can assess the impact of instructional changes. The evidence of instructional effectiveness can in turn inform future instruction, and vice versa. In this study, we analyzed student responses on an optimized pretest and posttest administered during four different quarters in a large-enrollment biochemistry course. Student performance and the effect of instructional interventions related to three fundamental concepts—hydrogen bonding, bond energy, and pKa—were analyzed. After instructional interventions, a larger proportion of students demonstrated knowledge of these concepts compared with data collected before instructional interventions. Student responses trended from inconsistent to consistent and from incorrect to correct. The instructional effect was particularly remarkable for the later three quarters related to hydrogen bonding and bond energy. This study supports the use of multiple-choice instruments to assess the effectiveness of instructional interventions, especially in large classes, by providing instructors with quick and reliable feedback on student knowledge of each specific fundamental concept.

scholarly journals Lanthanoid Complexes Supported by Retro-Claisen Condensation Products of β-Triketonates

2018 ◽  
Author(s):  
Laura Abad Galán ◽  
Alexandre N. Sobolev ◽  
Eli Zysman-Colman ◽  
Mark Ogden ◽  
Massimiliano Massi
Keyword(s):  
Chelating Ligands ◽  
X Ray Diffraction ◽  
Reaction Conditions ◽  
Claisen Condensation ◽  
X Ray ◽  
Condensation Products ◽  
Complexation Reactions ◽  
The Impact ◽  
Low Solubility

<i>β</i>-Triketonates have been recently used as chelating ligands for lanthanoid ions, presenting unique structures varying from polynuclear assemblies to polymers. In an effort to overcome low solubility of the complexes of tribenzoylmethane, four <i>β</i>-triketones with higher lipophilicity were synthesised. Complexation reactions were performed for each of these molecules using different alkaline bases in alcoholic media. X-ray diffraction studies suggested that the ligands were undergoing decomposition under the reaction conditions. This is proposed to be caused by <i>in situ</i>retro-Claisen condensation reactions, consistent with two examples that have been reported previously. The lability of the lanthanoid cations in the presence of a varying set of potential ligands gave rise to structures where one, two, or three of the molecules involved in the retro-Claisen condensationreaction were linked to the lanthanoid centres. These results, along with measurements of ligand decomposition in the presence of base alone, suggest that using solvents of lower polarity will mimimise the impact of the retro-Claisen condensation in these complexes. <br>

scholarly journals Noble-Metal-Free Photocatalytic Hydrogen Evolution Activity: The Impact of Ball Milling Anatase Nanopowders with TiH2

2016 ◽  
Vol 29 (5) ◽  
pp. 1604747 ◽  
Author(s):  
Xuemei Zhou ◽  
Ning Liu ◽  
Jochen Schmidt ◽  
Axel Kahnt ◽  
Andres Osvet ◽  
...  
Keyword(s):  
Ball Milling ◽  
Hydrogen Evolution ◽  
Noble Metal ◽  
Photocatalytic Hydrogen Evolution ◽  
Metal Free ◽  
The Impact

Evaluation of thermal and physical properties of PMMA/PMVEMA-ES blends as organic coating

2021 ◽  
Vol ahead-of-print (ahead-of-print) ◽  
Author(s):  
Shameer Hisham ◽  
Hairul Anuar Tajuddin ◽  
Norazilawati Muhamad Sarih ◽  
Nur Zarith Diana Diana Zakaria ◽  
Zul Hazrin Zainal Abidin ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Physical Properties ◽  
Organic Coating ◽  
Adhesion Property ◽  
Intermolecular Hydrogen Bonding ◽  
Scanning Calorimetry ◽  
Adhesion Promoter ◽  
Adhesion Properties ◽  
Content Type ◽  
The Impact

Purpose In this work, the blends of poly(methyl methacrylate), PMMA and poly(methyl vinyl ether-alt-maleic acid monoethyl ester), PMVEMA-ES are studied as organic coatings to evaluate the impact of intermolecular hydrogen bonding on the physical and thermal characteristics of the prepared coatings. Design/methodology/approach PMMA (Mw = 120,000 g mol-1) was chosen as our binder material. Due to the low adhesion property of PMMA on polar substrates, it was blended with PMVEMA-ES, which contains polar –COOH groups, to improve the adhesion and thermal properties of the coatings by forming intermolecular hydrogen bonds. A cross-hatch adhesion test was carried out to evaluate the adhesion strength of different ratios of PMMA/PMVEMA-ES blends as coatings. In addition, changes in the glass-transition temperature, Tg as the composition varies were studied using Differential Scanning Calorimetry, DSC. Then, glossiness and hiding power tests were also conducted to evaluate the physical properties of the prepared coatings. Findings Upon a closer look at the DSC results, it was found that blends consisting of 12.5, 25.0 and 87.5 wt. % PMMA were completely compatible due to the presence of only a single Tg in their thermograms. Other blend compositions showed two distinct Tgs, indicating partial compatibility. Furthermore, the addition of PMVEMA-ES caused the Tg of PMMA to shift to lower temperatures, a strong indication of intermolecular hydrogen bonding interactions between the two components. From the cross-hatch adhesion results, the addition of PMVEMA-ES improved the adhesion properties of PMMA coating, except for blends consisting of 62.5 and 75.0 wt. % PMMA possibly due to the partial incompatibility between the two components. These findings were further corroborated with the results of glossiness and hiding power measurements. The superior result was seen for the blend consisting of 12.5 wt. % PMMA with strong adhesion property, high glossiness, compatibility and high translucency. Practical implications PMVEMA-ES can potentially be used as an adhesion promoter in PMMA-based coating formulations. Originality/value This is the first report on the properties of PMMA/PMVEMA-ES blends as coatings.

scholarly journals Evidence for photosensitised hydrogen production from water in the absence of precious metals, redox-mediators and co-catalysts

2017 ◽  
Vol 19 (12) ◽  
pp. 8141-8147 ◽  
Author(s):  
S. Salzl ◽  
M. Ertl ◽  
G. Knör
Keyword(s):  
Hydrogen Production ◽  
Hydrogen Evolution ◽  
Precious Metals ◽  
Redox Mediators ◽  
Salt Solutions ◽  
Proton Reduction ◽  
Photocatalytic Hydrogen Evolution ◽  
Co Catalysts ◽  
Aqueous Salt Solutions ◽  
Earth Abundant

New approaches for sunlight-powered proton reduction and photocatalytic hydrogen evolution from aqueous salt solutions using earth-abundant components and molecular photosensitisers.

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