Article
Chemistry, Multidisciplinary
Nicolas Adet, David Specklin, Christophe Gourlaouen, Thibault Damiens, Beatrice Jacques, Rudolf J. Wehmschulte, Samuel Dagorne
Summary: The synthesis of Zn[HexCB(11)Cl(11)](2), 3, using the hexyl-substituted anion showed high catalytic activity in hydrosilylation reactions, attributed to its high solution Lewis acidity. This compound exhibited facile displacement of counterions and was characterized through various techniques including NMR, mass spectrometry, and DFT studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Tana Tana, Pengfei Han, Aidan J. Brock, Xin Mao, Sarina Sarina, Eric R. Waclawik, Aijun Du, Steven E. Bottle, Huai-Yong Zhu
Summary: 5-hydroxymethylfurfural (HMF) is a valuable platform chemical for sustainable fine-chemical and pharmaceutical industry based on biomass. The complex of fulvic acid with Al3+ ions exhibits solar absorption and photocatalytic activity for glucose conversion to HMF in one-pot reaction, offering prospects for new green photocatalytic systems. This mechanism creates the possibility of synthesizing a range of substances that have not previously been considered.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Liesa Eickhoff, Leon Ohms, Jonas Bresien, Alexander Villinger, Dirk Michalik, Axel Schulz
Summary: The formal coordination of phosphorus(III) was achieved by reacting a calix[4]pyrrole Schiff base ligand with PCl3 under basic conditions, resulting in a Pacman conformation reaction product. The spatial neighborhood of the two phosphorus atoms enables cooperative reactions, demonstrated by the chloride abstraction reaction with AgOTf to yield two embedded phosphorus(III) monocations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Energy & Fuels
Kai Sun, Yuewen Shao, Peng Liu, Lijun Zhang, Guoming Gao, Dehua Dong, Shu Zhang, Guangzhi Hu, Leilei Xu, Xun Hu
Summary: A solid salt catalyst FeClx-D008 was prepared by introducing FeCl3 onto a solid acidic resin D008, replacing some acid sites and improving catalytic selectivity for the production of furfural from C5 sugars.
Article
Green & Sustainable Science & Technology
M. Srida, S. -Y. Chen, S. M. Smith, C. Ngamcharussrivichai, S. Boonyuen, H. Tateno, T. Mochizuki, A. Luengnaruemitchai
Summary: This study prepared bifunctional solid acid catalysts composed of aluminum (Al) as Lewis acid sites and sulfonic acid (SA) as Bronsted acid sites by direct synthesis. These catalysts were evaluated for the conversion of glucose to 5-hydroxymethylfurfural (HMF) and the 5Al-15SA-S15 catalyst achieved 95% conversion of glucose and a 51% yield of HMF with good stability and reusability. This study provides important insights into the properties and applications of solid acid catalysts.
MATERIALS TODAY SUSTAINABILITY
(2023)
Article
Chemistry, Multidisciplinary
Matthew J. J. Genzink, Matthew D. D. Rossler, Herman Recendiz, Tehshik P. P. Yoon
Summary: Chiral acid catalysts are shown to promote highly selective visible-light photocycloadditions, leading to the synthesis of truxinate natural products. This general approach allows for the efficient synthesis of dimeric and pseudodimeric cyclobutane natural products with excellent enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Xie Zheng, Shijie Chen, Wanning Liu, Kaisong Xiang, Hui Liu
Summary: By modifying the HZSM-5 catalyst with Ce and sulfuric acid treatment, the conversion rate of CF4 can be greatly improved. The increase in acidic sites on the modified catalyst becomes the main active center for CF4 decomposition.
Article
Chemistry, Physical
Tingting Yan, Mengting Zhang, Runze Liu, Weili Dai, Naijia Guan, Landong Li
Summary: The selective conversion of the acetone-butanol-ethanol (ABE) mixture to high-valuable chemicals is still challenging. In this study, a bifunctional Ga/HZSM-5 zeolite catalyst containing both Bri nsted acid sites and Lewis acid sites was designed and used for the conversion of the ABE mixture to aromatics, achieving a state-of-the-art aromatics yield of 77%. The mechanisms of aromatics formation and catalyst deactivation were investigated, and a synergistic catalysis between Lewis acidic Ga species and Bri nsted acid sites was proposed.
Article
Chemistry, Multidisciplinary
Karel Skoch, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The compound undergoes a rare reaction with a borane to form a unique unsaturated compound, capable of reducing carbon monoxide and reacting with nitriles to produce a boron-containing heterocycle derivative.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Philip Netzsch, Regina Stroh, Florian Pielnhofer, Ingo Krossing, Henning A. Hoeppe
Summary: Borosulfates offer fascinating structures and properties beyond pure silicate analogy. Mg-3[H2O -> B(SO4)(3)](2) is the first borosulfate with a boron atom coordinated by three tetrahedra, exhibiting higher Lewis and Brønsted acidity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Energy & Fuels
Wei Lin, Ye Song, Lei Han, Xue Yang, Jun Liu, Bo Peng
Summary: In this study, 1-octene was used as a model compound to investigate its dehydrogenative aromatization over a series of Ni/ZSM5-based catalysts. The Ni/ZSM-5-P-Fe catalyst showed convincing catalytic performance with high conversion and selectivity, low coking, and satisfactory durability. The modification of P, Fe, and Ni on ZSM-5 was found to reduce Bronsted acid sites, generate new Lewis acid sites, and provide adequate metallic sites, which correlated well with the reaction results.
Article
Engineering, Environmental
Peng Lu, Lyumeng Ye, Xianhui Yan, Ping Fang, Xiongbo Chen, Dingsheng Chen, Chaoping Cen
Summary: The study examined the simultaneous removal of toluene in NH3-SCR reactions and found that MnCe/HZSM-5 catalyst with a SiO2/Al2O3 molar ratio of 25 exhibited superior catalytic performance. It was also discovered that toluene induced reversible catalyst deactivation in NH3-SCR reactions.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Deepamali Dissanayake, Alysia Draper, Zhizhou Liu, Neelofur Jaunnoo, Joris J. Haven, Craig Forsyth, Alasdair I. McKay, Tanja Junkers, Dragoslav Vidovic
Summary: A modest structural change in an aluminum complex leads to significant differences in reactivity towards cyclopentenone, with the larger complex executing Diels-Alder transformations and the smaller analogue undergoing unique polymerization.
Article
Chemistry, Multidisciplinary
Brandon L. L. Frenette, Jonathan Trach, Michael J. J. Ferguson, Eric Rivard
Summary: We report the stabilization of phosphinidenes (PR) by an intramolecular frustrated Lewis pair (FLP) chelate. Our new adducts, including PH accessed through thermolysis of coordinated HPCO, act as a starting point for other phosphorus-containing compounds. These adducts participate in thermal- or light-induced phosphinidene elimination, transfer P-2 units to an organic substrate, and yield the semiconductor InP at only 110 degrees C from solution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Heekyoung Choi, Soichiro Ogi, Naoki Ando, Shigehiro Yamaguchi
Summary: This study reports kinetically controlled supramolecular polymerization of boron-containing p-conjugated molecules using a seeding method based on dual trapping of a metastable state. The formation of helical supramolecular nanostructures with intense J-type aggregate emission was achieved through cooperative supramolecular polymerization. The presence of a Lewis acid-base complex enhanced the stabilization of the metastable monomeric state, allowing for successful production of homogeneous nanofibers even at high concentrations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xin Zhang, Hongyu Wang, Xiaofang Lan, Yanbo Mei, David A. Ruiz, Liu Leo Liu
Summary: Synthetic chemistry allows for the construction of molecular complexity using simple substrates and processes. We have developed an unprecedented aluminum atom transfer strategy for the synthesis of aluminum heterocycles with high atom economy. This strategy has significant implications for the design of future single-atom addition reactions and has paved the way for the development of luminescent materials based on aluminum heterocycles.
Article
Chemistry, Multidisciplinary
Ting Chen, Yanbo Mei, Liu Leo Liu, Yufen Zhao, Yile Wu, Douglas W. Stephan
Summary: The combination of alkoxyphosphoranes and borane generates zwitterions that act as FLP and can alkylate nucleophiles to form C-C, C-N, C-H, and C-Cl coupling products. A DFT study reveals that the reaction proceeds through an FLP activation pathway, forming an alkoxyphosphonium intermediate that facilitates the alkylation of nucleophiles, similar to the Mitsunobu reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Rui Wei, Xin-Feng Wang, David A. A. Ruiz, Liu Leo Liu
Summary: Under CO atmosphere, a (phosphino)diazomethyl anion salt (1) undergoes a facile N-2/CO exchange reaction to give a (phosphino)ketenyl anion salt (2). Further oxidation of (2) with elemental Se affords a (selenophosphoryl)ketenyl anion salt (3). The ketenyl anions exhibit a strongly bent geometry and high nucleophilicity. Reactivity investigations reveal the versatility of (2) as a synthon for various derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Xin Zhang, Liu Leo Liu
Summary: The reactivity of the free aluminylene [N]-Al (1) towards boron Lewis acids was studied. A rare example of the free alumaborane [N]-Al(BPh2)(OBPh2) (2) with an Al-B electron-sharing bond was formed by oxidative addition of 1 with Ph2BOBPh2. On the other hand, complexation of 1 with B(C6F5)(3) and HB(C6F5)(2) resulted in the corresponding Lewis adducts [N]-Al -> B(C6F5)(3) (3) and [N]-Al -> BH(C6F5)(2) (4) with an Al -> B dative bond. Crystallization of 4 in Et2O produced the adduct [N]-Al(Et2O)-> BH(C6F5)(2) (5). Quantum chemical calculations were performed to understand the formation of 2 and the bonding situation of 3 and 5.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Chaopeng Hu, Liu Leo Liu
Summary: We discovered a tris(carbene)borate (TCB) ligand that can stabilize an unprecedented nucleophilic Sn(II) cation salt. The strong electron-donating ability of [PhB-(tBuIm)3]- makes the cationic tin atom electron-rich, sigma-donating, and slightly pi-accepting, allowing for easy oxidation with o-chloranil and S8, as well as coordination with coinage metals. Quantum chemical computations were used to probe the electronic structures of these species. These findings reveal an additional role for TCB ligands in isolating unprecedented p-block species.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiwei Lv, Yuyang Dai, Rui Guo, Yuanting Su, David A. Ruiz, Liu Leo Liu, Chen-Ho Tung, Lingbing Kong
Summary: This report reveals an advancement in the formation of a Lewis superacid (LSA) and an organic superbase through the geometrical deformation of an organoboron species. The boron dication [2](2+) supported by an amido diphosphine pincer ligand exhibits strong Lewis acidic properties and is capable of catalyzing various reactions. Additionally, reduction of [2](2+) produces stable boron radical cation [2](center dot+) and borylene 2, which demonstrate high spin density and strong organic base properties, respectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Rui Guo, Chaopeng Hu, Qianli Li, Liu Leo Liu, Chen-Ho Tung, Lingbing Kong
Summary: This study presents a new isolable diiminoborane compound with a BN analogue of butadiyne structure, which can release and reduce N-2. This discovery has significant implications for the future design of functional main group N-2 species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jiong Zhang, Rui Wei, Chunping Ren, Liu Leo Liu, Lipeng Wu
Summary: This study reports the first Si-B functional group exchange reactions of hydrosilanes with hydroboranes, enabled by BH3 as a catalyst. The methodology shows applicability to various aryl and alkyl hydrosilanes and different hydroboranes, with tolerance to general functional groups. Further investigations demonstrate the use of chlorosilanes, siloxane, fluorosilane, and silylborane for Si-B functional group exchanges, Ge-B functional group exchanges, and depolymerizative Si-B exchanges of polysilanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: Cyclopropenium cations with electron deficient substituents exhibit Lewis acidity despite the presence of π-electrons. The chloride and electron affinities are analyzed computationally and experimentally, respectively. These cations form traditional Lewis acid-base adducts with PPh3, while sterically hindered phosphines lead to frustrated Lewis pairs that participate in FLP additions. Depending on the basicity of the phosphine, addition to alkynes or alkyne deprotonation can occur. In both cases, new C-C bonds are formed, thus expanding the application of FLP chemistry to these delocalized π-cations.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Douglas W. W. Stephan
Summary: Transition metal species readily capture and react with CO, while main group CO adducts and their subsequent reactivity have been less studied. This review focuses on the application of Frustrated Lewis Pairs (FLPs) to develop main group chemistry of CO, illustrating the ability to capture CO and subsequent reduction reactions. These developments suggest that FLPs provide an alternative strategy to enhance the reactivity of CO, promising future advances in homogeneous CO chemistry.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Zahid Hussain, Yong-An Luo, Yile Wu, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: The reactions of (tBuO(2)CN)(2) with FLPs were investigated. B(C6F5)(3) interacts with the carbonyl oxygen atoms and causes the loss of CH2=CMe2. However, in the presence of basic donors, the protons are intercepted and form salts [Hbase](2) [((C6F5)(3)BO2CN)(2)]. In the presence of (o-Tol)(3)P, a proton transfers to the diazo-N atom and forms (o-Tol)(3)PN(CO(2)tBu)NHB(C6F5)(3). Further addition of B(C6F5)(3) prompts the loss of olefin CH2=CMe2 and CO2, resulting in the formation of (o-Tol)(3)PNHNHB(C6F5)(3). DFT calculations provide insights into the reaction mechanisms and confirm the nature of 5 as a FLP reduction product of a diazene fragment.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Vaibhav Bedi, Dipendu Mandal, Zahid Hussain, Shi-Ming Chen, Yile Wu, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: The reaction of (tBuO(2)CN)(2) with 9-BBN leads to the formation of a bicyclic heterocyclic compound, while its reactions with BF3 or [Et3Si][B(C6F5)(4)] result in the isolation of different compounds. Computational studies reveal that the steric and electronic properties of the Lewis acid are important in the formation of one of the compounds.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Jixing Han, Chaopeng Hu, Qianli Li, Liu Leo Liu, Chen-Ho Tung, Ping Cui, Lingbing Kong
Summary: The synthesis and reactivity of alkylideneborane supported by N-heterocyclic imino and N-heterocyclic carbene ligands are presented. These ligands weaken the B=C bond strength, leading to enhanced reactivity. Selective cleavage and insertion reactions of the B=C bond were achieved, demonstrating the potential of alkylideneborane as a versatile building block for synthesizing novel organoboron compounds through unconventional transformations.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiancheng Li, Yanbo Mei, Xin-Feng Wang, Liu Leo Liu
Summary: The synthesis of phosphaborenes featuring an N-heterocyclic boryl group on phosphorus and halogen substituent on boron, with stabilization provided by an N-heterocyclic carbene, has been documented. This approach offers an efficient route to produce a diverse array of phosphaborene structures.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Xiaofang Lan, Xin Zhang, Yanbo Mei, Chaopeng Hu, Liu Leo Liu
Summary: In this study, we report the synthesis and characterization of an Sb(iii) monocation salt stabilized by a bulky bis(imino)dihydroacridanide pincer ligand. The Lewis acidity of the Sb cation is confirmed through quantitative analysis and reaction with 4-dimethylaminopyridine. The catalytic activity of this Sb cation in the cyanosilylation of arylketones as well as its electronic structure and mechanism are investigated using density functional theory computations.
DALTON TRANSACTIONS
(2023)
