Article
Chemistry, Multidisciplinary
Shao-Jie Lou, Qingde Zhuo, Masayoshi Nishiura, Gen Luo, Zhaomin Hou
Summary: The study demonstrates the highly enantioselective C-H alkenylation of quinoline- and pyridine-substituted ferrocenes with alkynes using a half-sandwich scandium catalyst. This method offers broad substrate scope, high enantioselectivity, and selectively affords a new family of planar-chiral ferrocenes bearing N/alkene functionalities. The use of a quinoline/alkene-functionalized ferrocene product as a chiral ligand for asymmetric catalysis is also showcased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Hui Liu, Suting Xu, Xiaochao Shi
Summary: The synthesis of half-sandwich chromium(III) complexes bearing ligands and their catalytic activities for ethylene polymerization to produce high molecular weight polyethylene were investigated in this study.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Yi Zhong, Min Li, Meng Deng, Mingliang Gong, Hongzhen Xie, Yunjie Luo
Summary: Redox-controlled polymerization is an efficient strategy for constructing precise microstructures of polymeric materials. In this study, a ferrocenyl functionalized half-sandwich scandium complex was successfully synthesized and used for redox-controlled polymerization of styrene.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Xin-Lei Li, Tie-Qi Xu
Summary: In this paper, the research progress of stereoselective polymerization catalysts for aromatic polar vinyl monomers in recent years is reviewed. The influence of ligand structure, electronic effect of substituents, spatial site resistance effect, central rare earth metal species, and polymerization solvents on the activity and stereoselectivity of polymerization reactions are discussed in detail, as well as the possible mechanism of polymerization reaction.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Engineering, Chemical
Ke Yang, Shanda Wang, Rifeng Zhou, Qingli Cheng, Quanguo Wang, Yang Li
Summary: This article describes a method of combining the advantages of syndiotactic polystyrene and polyisobutylene by introducing isobutylene into the polymer, forming graft copolymers with high strength and low glass transition temperature.
POLYMER ENGINEERING AND SCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
Thakur Rochak Kumar Rana, Abinash Swain, Gopalan Rajaraman
Summary: Chromium-based catalysts are important in the production of ultra-high molecular weight polyethylene, and half-sandwich functionalised-metallocene complexes are suitable catalysts for generating large polymeric-length olefins. Experimental studies have shown that peripheral substitution on the ligand affects the reactivity, but the specific ligand position is still unknown. Through computational study, we found that substituted pyridine-cyclo-pentadienyl chromium complexes influence catalytic activity in ethylene polymerisation, and the formation of pseudo-three-coordinate alkyl intermediates plays a key role in the observed reactivity variation. Agostic interactions should be considered as a crucial criterion in designing future catalysts to improve the efficiency and selectivity of olefin polymerisation.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Suting Xu, Yanchen Huo, Xiang Hu, Fei Wang, Li Pan, Xiaochao Shi
Summary: In this study, rare-earth metal complexes bearing tetrahydrofluorenyl ligands were synthesized and characterized. These complexes showed excellent catalytic activity for the polymerization of styrene and butadiene, resulting in diblock copolymers with highly syndiotactic polystyrene block and a 1,4-specific PBD block. The study also revealed the significant difference in reactivity ratios between butadiene and styrene, supporting the block structure of the copolymers. Morphology and mechanical properties of the selected diblock copolymer were investigated.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Alejandro Yanez-Cabrera, Jose Rosas-Galicia, Maribel Arroyo-Carranza, Armando Ramirez-Monroy
Summary: Half-sandwich Fe(II) complexes with chelating ligand 2-(diphenylphosphino)ethylamine were prepared successfully and their catalytic activity was evaluated, with compound 2 showing the highest activity and conversion.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Polymer Science
Yinran Wang, Lin Huang, Zhaomin Hou, Fang Guo
Summary: The polymerization of alpha-olefins and their copolymerization with ethylene by scandium catalysts with different ligands were studied. The ligands and linker length were found to have significant effects on the catalyst activity and resulting polymers. The research discovered that the scandium complex with un-linked fluorenyl and NHC ligands effectively inhibited beta-H elimination reaction in alpha-olefin polymerization, demonstrating quasi-living polymerization characteristics. However, its thermal stability was poor. On the other hand, scandium complexes with linked fluorenyl-NHC ligands with longer spacers showed improved thermal stability and efficient inhibition of beta-H elimination reaction, as well as high activity in alpha-olefin polymerization and copolymerization with ethylene.
Article
Chemistry, Organic
Xuefeng Cong, Lin Huang, Zhaomin Hou
Summary: This Perspective focuses on recent advances in C-H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts, including asymmetric transformations. The reaction generally proceeds through formal C-H addition to unsaturated C-C bonds, thus constituting a 100% atom-efficient route for the construction of new C-C bonds. Future outlooks in related areas are also described.
Article
Polymer Science
Chuang Song, Jupeng Chen, Zhijie Fu, Li Yan, Feng Gao, Qingbin Cao, He Li, Xiangqian Yan, Shilu Chen, Shaowen Zhang, Xiaofang Li
Summary: A scandium dication active species exhibits unprecedentedly high activity and syndiotactic selectivity in the polymerization of o-methoxystyrene, producing syndiotactic poly(oMOS)s with ultrahigh molecular weight not achievable by traditional catalysts.
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, Multidisciplinary
Benon P. Maliszewski, Tahani A. C. A. Bayrakdar, Perrine Lambert, Lama Hamdouna, Xavier Trivelli, Luigi Cavallo, Albert Poater, Marek Belis, Olivier Lafon, Kristof Van Hecke, Dominic Ormerod, Catherine S. J. Cazin, Fady Nahra, Steven P. Nolan
Summary: In this study, the catalytic activity of a series of platinum(II) pre-catalysts with N-heterocyclic carbene (NHC) ligands in the alkene hydrosilylation reaction is reported. The structural and electronic properties of these catalysts are fully characterized using X-ray diffraction analysis and nuclear magnetic resonance spectroscopy (NMR). A structure-activity relationship within this group of pre-catalysts is established, and mechanistic insights into the catalyst activation step are provided. One of the complexes shows exceptional catalytic performance, achieving a turnover number (TON) of 970,000 and a turnover frequency (TOF) of 40,417 h(-1) at 1 ppm catalyst loading. Furthermore, a solvent-free and open-to-air alkene hydrosilylation protocol with efficient platinum removal (reducing residual Pt from 582 ppm to 5.8 ppm) is disclosed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yu Cao, Ekaterina Toshcheva, Walid Almaksoud, Rafia Ahmad, Tatsuya Tsumori, Rohit Rai, Ya Tang, Luigi Cavallo, Hiroshi Kageyama, Yoji Kobayashi
Summary: In this study, we demonstrate the robust ammonia synthesis activity of the nitride hydride compound Ca3CrN3H, which activates dinitrogen through active sites where calcium provides the primary coordination environment. DFT calculations indicate that an associative mechanism is favored, unlike the dissociative mechanism found in traditional Ru or Fe catalysts. This work showcases the potential of alkaline earth metal hydride catalysts and other related 1D hydride/electrides for ammonia synthesis.
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
Chemistry, Multidisciplinary
Honghong Liang, Zheng Ma, Yuqi Wang, Fei Zhao, Zhen Cao, Luigi Cavallo, Qian Li, Jun Ming
Summary: This study achieves reversible lithium-ion (de)intercalation in a propylene carbonate (PC)-based electrolyte containing a fluoroether by tuning the solvent-solvent interaction, providing an opportunity to enhance the compatibility of PC-based electrolytes with graphite anodes.
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
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.