Article
Chemistry, Multidisciplinary
Mathis J. Benedikter, Janis V. Musso, Wolfgang Frey, Roman Schowner, Michael R. Buchmeiser
Summary: Despite their excellent selectivities and activities, Mo- and W-based catalysts for olefin metathesis have not been widely used due to their air sensitivity. The synthesized cationic-at-metal molybdenum and tungsten imido alkylidene NHC nitrile complexes are stable in air and can catalyze olefin metathesis reactions without prior activation. The presence of a nitrile ligand is crucial for their stability, while variations in imido and anionic ligands affect reactivities and stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jin Huang, Rui Yan, Yongwei Ni, Na Shi, Zhenjiang Li, Canliang Ma, Kai Guo
Summary: This study presents a method for synthesizing cyclic polycarbonates through zwitterionic ring-opening polymerization (ZROP) of macrocyclic carbonates, mediated by N-heterocyclic carbene (NHC). The synthesized cyclic polycarbonates exhibited improved thermostabilities compared to linear carbonates and the macrocyclic monomers could be regenerated through thermal depolymerization, achieving a closed loop of polycarbonate stream.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Hang Shen, Michael B. Larsen, Allison G. Roessler, Paul M. Zimmerman, Andrew J. Boydston
Summary: A new flex-activated mechanophore has been discovered, which releases an N-heterocyclic carbene (NHC) under mechanical load. This design demonstrates a promising first step towards flex-activated designs with downstream reactivities, allowing for iterative activation increases in the material through non-destructive compression cycles. The potential modularity of the mechanophore design is highlighted by the demonstration of two different NHC structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Zhen Li, Pengju Ji, Jin-Pei Cheng
Summary: A Brønsted basicity scale was established for nine representative N-heterocyclic olefins (NHOs) using an UV-visible spectroscopic method. The unsaturated NHOs were found to have stronger basicities compared to their N-heterocyclic carbene (NHC) analogues, while the basicities of the saturated NHOs were weaker. The nucleophilicity of the NHOs was also stronger than commonly used Lewis bases but weaker than their NHC analogues.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ludwig Zapf, Udo Radius, Maik Finze
Summary: The paper describes the synthesis of 1,3-bis(tricyanoborane)imidazolate anion and its derivatives, including a novel dianionic N-heterocyclic carbene. These compounds exhibit unique electronic and steric properties, making them promising ligands and building blocks for coordination chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This review article aims to highlight recent advances in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. The synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs) based on a 1,3-imidazole framework are also presented. iMICs and ADCs have the potential to push the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligand sets, and more.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Junbeom Park, Jaelim Kim, Gu Yoon Jeong, Youngsuk Kim, Eunsung Lee
Summary: This study investigates the electron and proton transfer chemistry of N-heterocyclic carbene nitric oxide radical compounds and prepares a variety of nitrosyl derivatives. The reactions of these derivatives resemble those of transition metal nitrosyl complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemical Research Methods
Fady Nahra, Nikolaos Tzouras, Alba Collado, Steven P. Nolan
Summary: N-heterocyclic carbene gold(I) chloride and hydroxide complexes are commonly used as synthetic reagents and efficient catalysts. This study describes a straightforward and practical method for synthesizing mononuclear gold complexes with high yields, as well as the synthesis of a mononuclear gold(I) hydroxide complex and an improved synthesis method for a dinuclear gold(I) hydroxide complex. This methodology offers advantages such as the use of sustainable reaction solvents and commercially available starting materials.
Review
Chemistry, Multidisciplinary
Tingting Li, Zhichao Jin, Yonggui Robin Chi
Summary: This review discusses N-heterocyclic carbene-catalyzed reactions for the formation of aromatic compounds, categorizing them into 4 types based on activation modes. The achievements, challenges, and future research directions in NHC-catalyzed arene construction processes are summarized. The outlook is based on the authors' opinions and knowledge on the trends of NHC organocatalysis development.
SCIENCE CHINA-CHEMISTRY
(2022)
Article
Chemistry, Organic
Kosuke Yasui, Miharu Kamitani, Hayato Fujimoto, Mamoru Tobisu
Summary: This study reports on the N-heterocyclic carbene (NHC)-catalyzed Truce-Smiles rearrangement of aniline derivatives, where an unactivated C(aryl)-N bond is cleaved to form a new C(aryl)-C bond. The key to the success of this reaction lies in the utilization of highly nucleophilic NFIC, which enables the formation of a highly nucleophilic ylide intermediate generated from an alpha,beta-unsaturated amide.
Review
Chemistry, Multidisciplinary
Kun-Quan Chen, He Sheng, Qiang Liu, Pan-Lin Shao, Xiang-Yu Chen
Summary: In recent years, NHC-catalyzed radical reactions have been gaining attention for their potential to create new activation modes previously inaccessible. Further research and understanding of this emerging area is warranted to explore its synthetic techniques and advantages.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Nadine Weyer, Myron Heinz, Julia I. Schweizer, Clemens Bruhn, Max C. Holthausen, Ulrich Siemeling
Summary: The N-heterocyclic silylene shows a remarkable combination of thermal stability and reactivity towards small molecules, producing different follow-up products in reactions with CO2, N2O, H2O, NH3, and FcPH(2). Unexpectedly, the reaction with H3BNH3 results in B-H activation instead of N-H activation. DFT results suggest dramatically different mechanisms for these H-X insertions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Theo Maulbetsch, Doris Kunz
Summary: The synthesis of a novel NHC-containing porphyrinoid ligand with good fluorescence properties was successfully achieved. Experimental results demonstrated that the heterocyclic moieties in both the ligand and its metal complexes exhibit aromatic character instead of antiaromatic macrocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Sebastien Le Roux, Guido Ori, Stephane Bellemin-Laponnaz, Mauro Boero
Summary: Metal carbene complexes are a common class of compounds in organometallic chemistry that can catalyze various reactions. The nature of the metallic ion has little impact on the structure of the ligand, but removing an electron can affect the ligand conformation and subsequently influence the catalytic properties of the complex.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Multidisciplinary Sciences
Pui-Ki Wan, Ka-Chung Tong, Chun-Nam Lok, Chunlei Zhang, Xiao-Yong Chang, Kong-Hung Sze, Alice Sze Tsai Wong, Chi-Ming Che
Summary: A metal complex, Pt1a, has been found to interact with vimentin and inhibit tumor growth and metastasis, showing promise as an effective targeted chemotherapy for combating metastatic cancers.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Multidisciplinary
Prajyot Jayadev Nagtilak, Manoj V. Mane, Supreeth Prasad, Luigi Cavallo, Dean J. Tantillo, Manmohan Kapur
Summary: This study reports the reactivity of propargyl alcohols as Three-Carbon Synthons in a Rh(III)-catalyzed C-H functionalization. This method allows for the efficient synthesis of diverse molecular frameworks, with good functional group tolerance and unique regioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yury Minenkov, Luigi Cavallo, Kirk A. Peterson
Summary: The impact of complete basis set extrapolation schemes, diffuse functions, and tight weighted core functions on predicted enthalpies of formation via the DLPNO-CCSD(T1) approach has been investigated for neutral H,C,O-compounds. The results show that all tested extrapolation schemes have a mean unsigned deviation below 2 kJ mol(-1) relative to the experiment. The influence of tight weighted core functions on atomization energies is small, and core-valence correlation effects converge at triple-zeta level. The effect of diffuse function augmentation converges slowly and cannot be reproduced accurately with double-zeta or triple-zeta calculations.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Long Huang, Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo, Magnus Rueping
Summary: In this study, stereodivergent allylic C(sp(3))-H bond arylations were successfully developed through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. Unlike the typical photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrated the feasibility of switching the C-C double bond stereoselectivity through ligand control and steric and electronic effects.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jennifer Morvan, Francois Vermersch, Ziyun Zhang, Thomas Vives, Thierry Roisnel, Christophe Crevisy, Laura Falivene, Luigi Cavallo, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: The development of highly efficient enantioselective olefin metathesis catalysts is a major challenge. By using optically pure chiral cyclic (alkyl)(amino)carbene (ChiCAAC) ligands and preliminary mechanistic insights and density functional theory (DFT) computations, it was observed that the formation of rotamers before the enantio-determining step can impair catalytic performances in this field. DFT calculations also demonstrated that these findings can help accelerate ligand discovery by providing faster methods to differentiate potential candidates.
Article
Chemistry, Physical
Manoj V. Mane, Sayan Dutta, Luigi Cavallo, Bholanath Maity
Summary: In recent years, there has been a growing interest in multicomponent reactions (MCRs) as environmentally friendly and reliable synthetic strategies for drug discovery. This article discusses theoretical investigations that unravel the mechanistic pathways in IrIII-CuII dual-catalyzed MCRs, experimentally reported by MacMillan, and explains the origin of selectivity between three-component and two-component coupling products. The results suggest that N-H bond activation is the rate-limiting step and the preference for a two-component product is governed by the relative stabilities of the CuII-X center dot intermediates.
Article
Chemistry, Physical
Zahra Almisbaa, Hassan A. Aljama, Khalid Almajnouni, Luigi Cavallo, Philippe Sautet
Summary: DFT-based reaction profiles and microkinetic simulations were used to investigate the selective hydrogenation of acetylene on Ni-based intermetallic catalysts. Among the tested catalysts, NiIn showed the highest ethylene yield, while NiIn and Ni2In3 exhibited reduced ethane formation and increased oligomerization compared to Ni and Ni3In. The findings emphasize the importance of considering oligomerization reactions and coverage effects when evaluating the selectivity of catalysts. Additionally, the presence of indium on the catalytic surface was found to decrease the rate of acetylene consumption, highlighting a trade-off between activity and selectivity.
Article
Chemistry, Physical
Yuqi Wang, Zhen Cao, Zheng Ma, Gang Liu, Haoran Cheng, Yeguo Zou, Luigi Cavallo, Qian Li, Jun Ming
Summary: We detected the presence of weak solvent-solvent interactions in electrolytes using nuclear magnetic resonance and found that these interactions play a significant role in stabilizing the electrolytes, which is a novel discovery. By studying the role of ethylene carbonate (EC) solvent in lithium-ion battery electrolyte, we found that EC can stabilize linear carbonate solvent electrolyte, particularly diethyl carbonate (DEC), through weak intermolecular interactions, enhancing the energy difference between the orbitals of the Li+(EC)(x)(DEC)(y) complex and demonstrating strong capability against reduction. Our findings were further confirmed in other metal ion batteries (e.g., Na+, K+), highlighting the importance of electrolyte design and deeper understanding of battery performance.
ACS ENERGY LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Arijit Das Sharma, Ravneet Kaur Grewal, Suresh Gorle, Andres Felipe Cuspoca, Vikas Kaushik, Abdul Rajjak Shaikh, Luigi Cavallo, Mohit Chawla
Summary: Gastrointestinal diarrhea, mainly caused by rotavirus, is a highly contagious disease with high mortality rates, especially in developing countries. The available vaccines have limited efficacy and there are risks associated with vaccination. Therefore, the development of alternative vaccines is necessary.
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2023)
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Krishnamoorthy Muralirajan, Rajesh Kancherla, Bholanath Maity, Safakath Karuthedath, Frederic Laquai, Luigi Cavallo, Magnus Rueping
Summary: In this manuscript, the authors describe the development of excited-state Pd-catalyzed dehydrogenative beta-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C-S cross-coupling processes at room temperature. The reaction efficiently converts amines into stable sulfonyl-substituted enamines and provides evidence for both static and dynamic quenching, as well as inner-sphere and outer-sphere mechanisms.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Xingzhu Chen, Luigi Cavallo, Kuo-Wei Huang
Summary: In the past decade, density functional theory (DFT) calculations have been used to investigate the mechanism of electrochemical CO2 reduction reactions. However, the lack of understanding regarding CO2 chemisorption states, proton-coupled-electron-transfer (PCET) steps, and dynamic redox reactions of the electrode surface has limited the reliability of these simulations. This work proposes a descriptor, the energy difference between *COOH on neutral and extra-electron substrates, as a means to determine the selectivity of electrochemical CO2 reduction.
Review
Chemistry, Multidisciplinary
Bholanath Maity, Sayan Dutta, Luigi Cavallo
Summary: C-sp3-C cross-coupling, a dream reaction in the chemical community, can be achieved by activating C-sp3-H bonds through visible light-induced transition metal-catalysis under mild reaction conditions. However, this research area is still in its early stages due to the chemical and technical complexity of this catalysis. Complementary experimental and theoretical mechanistic studies are essential for rational advances, as each approach alone is inadequate to clarify the operative mechanisms. In this tutorial review, we summarize representative experimental and computational mechanistic studies, highlighting the weaknesses, strengths, and synergies between the two approaches.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sofie M. P. Vanden Broeck, Nikolaos V. V. Tzouras, Marina Saab, Kristof Van Hecke, Busra Dereli, Ida Ritacco, Luigi Cavallo, Georgios C. C. Vougioukalakis, Pierre Braunstein, Steven P. P. Nolan, Andreas A. A. Danopoulos, Catherine S. J. Cazin
Summary: The 4-RN-1,3-Ar-2-imidazolium salt, R = iPr, tBu, Ar = Mes, Dipp, underwent metalation by Au-I at the C2-, C5-, and 4-RN positions, depending on the reactants and conditions used. A rare direct rearrangement of the Au-I aminide to an abnormal imidazol-5-ylidene Au-I complex was also observed, which may involve TfO- facilitated H+ transfer, according to a DFT study.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ekaterina A. Martynova, Marco Zuccarello, Domenic Kronenberg, Marek Belis, Agnieszka Czapik, Ziyun Zhang, Kristof Van Hecke, Marcin Kwit, Olivier Baudoin, Luigi Cavallo, Steven P. Nolan
Summary: Green and sustainable access to chiral and achiral gold-IBiox complexes is achieved through a simple and air-tolerant synthesis method using a green solvent. The catalytic activity of these complexes in the hydroamination of alkynes is examined, and their steric protection of the gold center is compared with commonly encountered NHCs using the %V-bur model.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Bo Li, Liang Yi, Bholanath Maity, Jiaqi Jia, Yuqin Shen, Xiang-Yu Chen, Luigi Cavallo, Magnus Rueping
Summary: Noncovalent interactions, particularly halogen bonding, play a crucial role in organic synthesis and catalysis, including the synthesis of organoselenium compounds. By utilizing the reaction balance between an electron donor-acceptor complex and Ph2Se2, the halogen bonding interaction facilitates the formation of C-Se bonds through the capture of alkyl radicals. This synthetic strategy has been successfully applied in the transformation of various carboxylic acids, natural products, drugs, and alpha-selenoamino acids.
