Publications related to Migratory insertion

Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49Ti Solid-State Nuclear Magnetic Resonance Spectroscopy

Treatment of Ziegler-Natta (ZN) catalysts with BCl3 improves their activity by increasing the number of active sites. Here we show how Ti-47/49 solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of t ...

Amer Chemical Soc2024

Probing Catalytic Sites and Adsorbate Spillover on Ultrathin FeO2-x Film on Ir(111) during CO Oxidation

Harald Brune, Hao Yin, Wei Fang

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising pote ...

Amer Chemical Soc2024

A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes

Rosario Scopelliti, Marinella Mazzanti, Ivica Zivkovic, Dieuwertje Katelijn Modder

Herein, we report the redox reactivity of a multimetallic uranium complex supported by triphenylsiloxide (−OSiPh3) ligands, where we show that low valent synthons can be stabilized via an unprecedented mechanism involving intramolecular ligand migration. T ...

Wiley-VCH Verlag GmbH2023

Implementing Multi-Electron Transfer Strategies in Uranium Chemistry

Dieuwertje Katelijn Modder

In the last decades, the activation of small molecules has attracted increasing attention for their use as cheap and abundant feedstock. Low-oxidation state uranium complexes have displayed high reactivity towards small molecules thanks to their unique pro ...

EPFL2023

Two-Carbon Ring Expansion of Cyclobutanols to Cyclohexenones Enabled by Indole Radical Cation Intermediate: Development and Application to a Total Synthesis of Uleine

Qian Wang, Jieping Zhu, Alexandre Julien Florent Leclair

A single-electron transfer (SET) oxidation of indole or benzo[b]thiophene to a radical cation reverses the intrinsic polarity of these pi-excessive bicyclic heteroarenes. Here we report an oxidative two-carbon homologation of cyclobutanols to cyclohexenone ...

AMER CHEMICAL SOC2022

Modular Synthesis of Benzocyclobutenes via Pd(II)-Catalyzed Oxidative [2+2] Annulation of Arylboronic Acids with Alkenes

Qian Wang, Jieping Zhu, Anne-Clémence Corminboeuf, Takuji Fujii, Simone Gallarati

Benzocyclobutenes (BCBs) are highly valuable compounds in organic synthesis, medicinal chemistry, and materials science. However, catalytic modular synthesis of functionalized BCBs from easily accessible starting materials remains limited. We report herein ...

2022

Simultaneous Generation of Methyl Esters and CO in Lignin Transformation

Paul Joseph Dyson, Mingyang Liu

Lignin is an abundant renewable carbon source. Due to its complex structure, utilization of lignin is very challenging. Herein, we describe an efficient strategy for the simultaneous utilization of lignin, in which the methoxy groups in lignin react with c ...

Wiley-VCH Verlag GmbH2022

The Genesis of Molecular Volcano Plots

Matthew Wodrich, Anne-Clémence Corminboeuf, Michael Markus Busch, Boodsarin Sawatlon

For the past two decades, linear free energy scaling relationships and volcano plots have seen frequent use as computational tools that aid in understanding and predicting the catalytic behavior of heterogeneous and electrocatalysts. Based on Sabatier's pr ...

2021

Carbon Dioxide Reduction by Multimetallic Uranium(IV) Complexes Supported by Redox-Active Schiff Base Ligands

Rosario Scopelliti, Marinella Mazzanti, Marta Falcone, Nadir Jori

The synthesis, structure, and reactivity with CO2 and CS2 of new U(IV) complexes with a redox-active Schiff base are reported. The reaction of UI3 with the heptadentate Schiff base ligand 2,2',2 ''-tris(salicylideneimino)-triethylamine (trensal) did not le ...

2020

Copper(I) Based Photoredox Chemistry

Murat Alkan

Photoredox catalysis has become a powerful tool for chemists. However, the reliance on expensive Ir and Ru based photoredox catalysts (PC) motivates research for more sustainable options. Copper complexes based on favorable photophysical properties, high a ...

EPFL2020

Uncertainty and sensitivity analysis of PWR mini-core transients in the presence of nuclear data uncertainty using non-parametric tolerance limits

Andreas Pautz, Winfried Zwermann, Alexander Aures

The impact of nuclear data uncertainties is studied for the reactor power and the reactivity during control rod withdrawal transients with reactivity insertions of 0.5

and 0.97

, respectively, for a PWR mini-core model. Multi-group cross sections, the mul ...

PERGAMON-ELSEVIER SCIENCE LTD2020

Synthetic Studies toward Amanita Phalloides Toxins

Philipp Georg Werner Seeberger

Amatoxins are ribosomally synthesized and post-translationally modified bicyclic octapeptides biosynthesized by the deadly basidiomycete fungus Amanita phalloides. Amongst this group, alpha-amanitin is the most widely known toxin and is currently under inv ...

EPFL2020

Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C-H Functionalizations

Nicolai Cramer, Yun-Suk Jang, Kristers Ozols

The synthesis of a set of cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric and electronic parameters are mapped. The application potential of these complexes for asymmetric C-H functionalizati ...

2019

Multidimensional Characterization of Mixed Ligand Nanoparticles Using Small Angle Neutron Scattering

Francesco Stellacci, Quy Ong Khac, Stefan Guldin, Zhi Luo, Ye Yang

The properties of ligand protected gold nanoparticles are determined by the synergistic interplay of their structural components, including the metal core, the ligand shell, and the solvation layer. However, the simultaneous characterization of all these c ...

AMER CHEMICAL SOC2019

In Situ Tethering Strategies for the 3-Component Synthesis of Vicinal Amino Alcohols and Diamines via Pd-Catalyzed Carboetherification and Carboamination

Ugo Jonathan Orcel

Vicinal amino alcohols and diamines are privileged motifs in organic chemistry. As such, they have been targets of choice for exploring and developing novel and more efficient strategies in organic synthesis. In this context, the difunctionalization of ole ...

EPFL2017

Synthesis of Diversely Functionalized Oxindoles Enabled by Migratory Insertion of Isocyanide to a Transient σ-Alkylpalladium(II) Complex

Qian Wang, Jieping Zhu, Wangqing Kong

Palladium-catalyzed intramolecular carbopalladation of N-aryl acrylamides followed by migratory insertion of an isocyanide-coordinated C(sp3)-Pd intermediate afforded an alkylimidoyl-Pd(II) complex, which can be intercepted by a nucleophile, including hete ...

Wiley-Blackwell2016

Rh(III)-Catalyzed C-H Functionalizations as Strategies for Versatile Organic Building Blocks

Van Manh Pham

Transition-metal catalyzed C-H functionalizations have impacted and changed synthetic approaches towards the construction of relevant complex molecules, comprising natural products, active pharmaceutical ingredients, and organic materials. This thesis desc ...

EPFL2016

CO2 conversion to isocyanate via multiple N–Si bond cleavage at a bulky uranium(III) complex

Marinella Mazzanti, Lucile Sylvie Danielle Chatelain

The reaction of the sterically saturated uranium(III) tetrasilylamido complex [K(18c6)][U(N(SiMe3)(2))(4)] with CO2 leads to CO2 insertion into the U-N bond affording the stable U(IV) isocyanate complex [K(18c6)]U(N(SiMe3)(2))(3)(NCO)(2) that was crys ...

Royal Society of Chemistry2015

Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes

Xile Hu, Thomas Clément Di Franco, Alexandre Epenoy

The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal ...

American Chemical Society2015

Catalytic Applications and Mechanistic Investigations of Iron Bis(oxazolinylphenyl)amino Pincer Complexes in Kumada Cross Coupling and Hydrosilylation Reactions

Gerald Bauer

The aim of the project was to investigate iron bis(oxazolinylphenyl)amino (bopa) pincer complexes as pre-catalysts in the enantioselective Kumada cross-coupling of non-activated alkyl halides with aryl Grignard reagents. From this preliminary cross-couplin ...

EPFL2015