Article
Chemistry, Inorganic & Nuclear
Licheng Zhan, Mingqiu Zhu, Lin Liu, Jiwei Wang, Congyun Xie, Jun Zhang
Summary: Heterotrimetallic complexes containing N-heterocyclic carbene have been synthesized and structurally characterized for the first time, showing carbene character of the donor groups in the tritopic NHC complexes through structural and NMR analyses.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Bennett J. Eleazer, H. D. A. Chathumal Jayaweera, Gayathri B. Gange, Mark D. Smith, Corey R. Martin, Kyoung Chul Park, Alexey A. Popov, Dmitry Peryshkov
Summary: The synthesis of well-defined heterometallic complexes is a challenging frontier in inorganic chemistry. A new approach involving sequential insertion of electrophilic metal fragments into electron-rich Ru-B bonds has been reported, leading to the selective preparation of bimetallic and trimetallic complexes. Structural and theoretical analysis of chemical bonding features within Ru-B-B-Cu and Ru-B-B-Pd fragments were presented.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Nils Lau Nyborg Broge, Andreas Dueholm Bertelsen, Frederik Sondergaard-Pedersen, Bo Brummerstedt Iversen
Summary: High-entropy alloys (HEAs) are a promising class of materials with extraordinary properties and customization potential through stoichiometry changes. This study presents a solvothermal method for synthesizing eight-component Pt-Ir-Pd-Rh-Ru-Cu-Ni-Co nano-HEA nanoparticles, which can be produced in large quantities. The method relies on simple autoclaves and in situ X-ray scattering experiments suggest auto-catalyzed growth of the particles, extending understanding of HEA nanomaterials.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Nikolai F. Romashev, Pavel A. Abramov, Ivan Bakaev, Iakov S. Fomenko, Denis G. Samsonenko, Alexander S. Novikov, Kelvin K. H. Tong, Dohyun Ahn, Pavel Dorovatovskii, Yan Zubavichus, Aleksey A. Ryadun, Olga A. Patutina, Maxim N. Sokolov, Maria Babak, Artem L. Gushchin
Summary: A series of Pt and Pd complexes with dpp-Bian and different ligands were synthesized and characterized. The Pt(dpp-Bian) complexes showed high anticancer activity at low concentrations and exhibited selectivity towards cancer cells. These complexes induced the generation of reactive oxygen species in cancer cells and were able to intercalate into DNA.
INORGANIC CHEMISTRY
(2022)
Article
Engineering, Environmental
Yang Guo, Haoran He, Xu Liu, Zhifeng Chen, Robert M. Rioux, Michael J. Janik, Phillip E. Savage
Summary: The study found that for hydrothermal HDN reaction, Ru is more active than Ni in the indole ring-opening and o-toluidine deamination reactions. When a hydrogen source is added, the pyrrole ring hydrogenates first to form indoline, followed by cleavage of the C-N bond.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Organic
Wen-Qiang Cai, Qi Wei, Qing-Wei Zhang
Summary: The nickel-catalyzed benzylic substitution reaction of secondary phosphine oxide was described, providing dialkylated P-stereogenic tertiary phosphine oxides with high to excellent enantioselectivities. The reaction was performed under mild conditions using commercially available benzyl chlorides and bench-stable secondary phosphine oxides, and exhibited broad functional group tolerance. This work represents a practical example for the preparation of P-stereogenic phosphine compounds.
Article
Chemistry, Physical
Shedrack G. Akpe, Sun Hee Choi, Hyung Chul Ham
Summary: This study used DFT techniques to investigate the conversion of xylose to xylitol on five notable transition metal surfaces, revealing that the structural rearrangement of cyclic xylose into its acyclic form is the starting process of the reaction.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexander Haseloer, Luca Mareen Denkler, Rose Jordan, Max Reimer, Selina Olthof, Ines Schmidt, Klaus Meerholz, Gerald Hoerner, Axel Klein
Summary: A study on new tetradentate phenolate (ONNS)-N-boolean AND-N-boolean AND-S-boolean AND thiosemicarbazone (TSC) ligands and their Ni(ii), Pd(ii) and Pt(ii) complexes was conducted. Density functional theory calculations, UV-vis spectroelectrochemistry, and UV-vis absorptions modeled through TD-DFT calculation showed details of molecular structures and electrochemical properties of the complexes. Ultraviolet photoelectron spectroscopy (UPS) results were consistent with UV-vis absorption, demonstrating decreasing HOMO-LUMO gaps along the series Pd > Pt > Ni.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Jianhua Song, Xiaoping Wang, Lin Xu, Chonghao Chen, Dianhua Liu
Summary: The efficient homogenous catalysis and spontaneous heterogeneous separation of Pd-catalyzed alkoxycarbonylation have been achieved using a rationally designed natural metabolite based acidic deep eutectic solvent (DES) as an acid co-catalyst. This approach improves the catalyst lifespan and operational efficiency.
Article
Chemistry, Inorganic & Nuclear
Matias E. Gutierrez Suburu, Ivan Maisuls, Jutta Kosters, Cristian A. Strassert
Summary: A series of Pd(II) and Pt(II) complexes with tetradentate ligands were synthesized as luminophores. Incorporation of these complexes into a polymeric matrix can enhance their photophysical properties.
DALTON TRANSACTIONS
(2022)
Article
Engineering, Environmental
Rok Sivec, Matej Hus, Blaz Likozar, Miha Grilc
Summary: In this study, the hydrogenation, hydrodeoxygenation, and ring opening of biomass-derived furfural were investigated using different catalysts. Pd/C was found to be the most active catalyst, while other catalysts exhibited selective aldehyde group hydrogenation and deoxygenation reactions. Thermodynamically, selective hydrogenation and deoxygenation were also favorable. By optimizing the reaction conditions, high yields of the desired products were obtained.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Sanya Pachisia, Ram Kishan, Samanta Yadav, Rajeev Gupta
Summary: This study reports the synthesis and characterization of two half-sandwich Ru(II) complexes supported with amide-phosphine based ligands, which serve as significant catalysts for the borohydride mediated reduction of various nitro-substrates. Mechanistic studies have confirmed the intermediacy of [Ru-H] in the reduction and asserted the involvement of several organic intermediates during the catalysis.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Toni Eskelinen, Stefan Buss, Stanislav K. Petrovskii, Elena Grachova, Maren Krause, Lukas Kletsch, Axel Klein, Cristian A. Strassert, Igor O. Koshevoy, Pipsa Hirva
Summary: The study synthesized and studied a series of cyclometalated complexes with an organometallic ligand of the group 10 metals (Ni, Pd, and Pt). Through combined experimental and computational approaches, the complexes were characterized in crystallography, showing dimer formation in the solid state with short metal-metal contacts. The computational models addressed both monomeric and dimeric entities, investigating their geometries, excited states, and electronic transitions.
INORGANIC CHEMISTRY
(2021)
Article
Agricultural Engineering
Kristaps Malins, Ilze Malina
Summary: Screening tests were conducted to evaluate the activity, selectivity, and potential of supported commercial and prepared Pd, Pt, Re, Rh, Ru, Ir, Au (5%), and Ni (5-65%) metal catalysts for renewable hydrocarbon production. The catalysts were characterized using various methods, and product composition was analyzed. The most active supported commercial Ni (65%) and Re, Rh, Ru (5%) catalysts achieved full conversion of rapeseed oil with a high renewable hydrocarbon yield in short reaction times under mild conditions. A novel Ru catalyst showed promising potential for practical application in renewable hydrocarbon synthesis by cleaving -C-C bonds and modifying different raw materials.
BIOMASS & BIOENERGY
(2023)
Article
Chemistry, Multidisciplinary
Mohamed F. Aly Aboud, Zeid A. ALOthman, Abdulaziz A. Bagabas
Summary: The research focused on improving hydrogen storage performance of activated carbon through methods like ammonia treatment and metal decoration. It was found that metal decoration had different effects on hydrogen storage at different temperatures, potentially overcoming hydrogen spillover at low temperatures but having the opposite effect at room temperature.
APPLIED SCIENCES-BASEL
(2021)
Article
Materials Science, Multidisciplinary
Anderson Hoff, Mark Martell, Akpeko Gasonoo, Josh D. B. Koenig, Pablo Simon Marques, Edward Cieplechowicz, Majid Pahlevani, Gregory Charles Welch
Summary: Herein, series bay position-substituted N-annulated perylene diimide (N-PDI) derivatives were used as the cathode interlayer in bottom-anode organic solar cells. By using ethyl acetate as a processing solvent, dissolved N-PDIs were able to form homogeneous films on the organic photoactive layer, resulting in improved power conversion efficiency from 8.5% to 12.5%. The smooth film morphology and high electron extraction capability of N-PDI are attributed to the enhanced performance of the cells.
ADVANCED ENGINEERING MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Zahid Hussain, Yong-an Luo, Yile Wu, Douglas W. W. Stephan
Summary: The reactions of boranes with azodicarboxylates or azodicarbonylamide provide easy access to NBO heterocyclic compounds. The formation mechanism is proposed to involve transient hydroboration or hydroalumination of the N=N double bond.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jingjie Tan, Chaopeng Hu, Xin Yang, Shaoying Ju, Levy L. Cao, Yile Wu, Liu Leo Liu, Douglas W. Stephan
Summary: The aluminum analogue of Piers' borane, [HAl(C6F5)(2)](3)1, was prepared on a gram-scale. DFT calculations showed that 1 has a higher fluoride ion affinity (FIA) than Piers' borane, and the Al-H moiety proved to be a strong hydride donor, reacting with alcohol and terminal alkyne to give dehydrogenative products 3 and 4. Hydroalumination product 5 was obtained via the reaction of 1 with aldehyde. Additionally, 1 catalyzes the hydrosilylation of alkynes and alkenes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Josh D. B. Koenig, Anderson Hoff, Akpeko Gasonoo, Gregory C. Welch
Summary: We studied the optoelectronic properties of four new pi-conjugated materials, which have different aryl cores and endcaps. The choice of endcap determines the molecular geometry, with NPDI endcaps inducing a dragonfly-type conformation and theobromine endcaps promoting a corkscrew-like conformation. The aryl core choice affects the highest occupied molecular orbital (HOMO) energy level, while the endcap choice has a greater impact on the lowest unoccupied molecular orbital (LUMO) energy level. The optical absorption profiles are mainly influenced by the endcaps, but using a larger aryl core decreases the optical energy band gap. Organic photovoltaic devices using these materials as the cathode interlayer (CIL) achieved power conversion efficiencies (PCEs) of around 12% for A and B (EDOT aryl core) and 10.5% for C and D (EDOT-flanked benzothiadiazole aryl core). The differences in device performance were attributed to solubility and film formation, leading to improved contact with the photoactive layer.
CHEMISTRY OF MATERIALS
(2023)
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
Pandeng Li, Anderson Hoff, Akpeko Gasonoo, Muhammad R. Niazi, Maryam Nazari, Gregory C. Welch
Summary: The traditional methods for manufacturing organic solar cells (OSCs) are not compatible with large-scale roll-to-roll production and use non-ecofriendly solvents. This study successfully developed slot-die coated OSCs using non-halogenated solvents, which improved efficiency and storage stability.
ADVANCED MATERIALS INTERFACES
(2023)
Editorial Material
Chemistry, Multidisciplinary
Zahid Hussain, Yong-an Luo, Yile Wu, Zheng-wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: Interest in main group chemistry related to the Haber-Bosch process is less studied compared to transition metal species. In this study, steric demands in (tBuO(2)CN)(2) hinder the initial interaction of B(C6F5)(3) with nitrogen, leading to the loss of methylpropene and CO2 and the formation of diazene (N2H2) borane adduct 1 and the analogous hydrazine (N2H4) adduct 2. These species react with basic phosphines to form anions of 3 and 5, which contain N2H and N2H3 fragments and serve as metal-free models of plausible intermediates in N-2 reduction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hyehwang Kim, Zheng-wang Qu, Stefan Grimme, Nahil Al-Zuhaika, Douglas W. Stephan
Summary: The phosphino-phosphonium cations can react with alkynes through frustrated Lewis pair-type addition reactions, leading to phosphino-phosphination reactions. This reactivity can also be utilized to prepare dissymmetric cis-olefin-linked bidentate phosphines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Ting Chen, Shaoying Ju, Mengnan Tong, Yufen Zhao, Yile Wu, Douglas W. Stephan
Summary: Metal phosphates are significant in the field of synthesis chemistry. In this study, we synthesized and characterized phosphate-catecholate chelated Nd(III), Zr(IV), and Al(III) chlorides (2-5). These complexes were obtained via ethyl chloride elimination reaction of oxophosphoranes with corresponding metal chlorides. The resulting monometallic and bimetallic phosphate-catecholate chelated metal complexes, stabilized by P-O and catecholate-O donors, have potential applications in catalysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(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
Hyehwang Kim, Douglas W. Stephan
Summary: A combination of a phosphinidene precursor, B(C6F5)(3), and 4-ethynyltoluene produced the FLP addition product, Et2N(C14H10)PC(Tol)=CH(B(C6F5)(3))2. Compound 2 reacted with halides, pseudo halides, or Me3SiSPh, providing an easy method for synthesizing salts of anionic phosphines, while the reaction with PEt3 resulted in the zwitterionic species, Et3PCH=C(SiMe3)P(NEt2)C(Tol)=CHB(C6F5)(3)8. This latter species reacted with an alkyne, yielding a phosphine donor with both olefin linked cationic and anionic substituents.
DALTON TRANSACTIONS
(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, Organic
Jiangkun Xiong, Maying Yan, Lvnan Jin, Weihong Song, Lei Xiao, Dong Xu, Chunyang Zhai, Douglas W. Stephan, Jing Guo
Summary: In this study, a new reaction method was reported for the synthesis of various organogermacycle compounds via a B(C6F5)(3) mediated domino hydrogermylation reaction of enones with dihydrogermanes. These germacyclic compounds were obtained in good to excellent yields under mild reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
