Article
Chemistry, Multidisciplinary
Iori Inoue, Koji Yamamoto, Shigeyoshi Sakaki, Tetsuro Murahashi
Summary: The formation of a heterometallic M-M' bond is crucial in constructing atomically precise bimetallic clusters and materials. By utilizing a sandwich framework of pi-conjugated unsaturated hydrocarbon ligands, a unique coordination environment is created that facilitates the unusual coupling of d(8) Rh-I and d(10) M-O (M=Pd, Pt), allowing the formation of a d sigma-type Rh-Pd bond.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Emi Ito, Shinjiro Takano, Toshikazu Nakamura, Tatsuya Tsukuda
Summary: Targeted syntheses of MM ' Au-36(PET)(24) were achieved through hydride-mediated fusion reactions, resulting in bi-icosahedral MM ' Au-21 cores composed of M@Au-12 and M '@Au-12 superatoms. Counterintuitive results were explained by a bent bonding model based on tilted bonding interaction between the superatomic orbitals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Guohai Deng, Yan Lu, Tony Stueker, Sebastian Riedel
Summary: Pd and Pt atoms react with NF3 to form N-coordination M(NF3) complexes in solid neon and argon matrices. Upon blue LED light irradiation, the M(NF3) complexes isomerize to more stable FNMF2 isomers by experiencing fluorine migration. These products are characterized using infrared absorption spectroscopy and theoretical frequency calculations with isotopic substitutions. The electronic structure analysis shows that the bonding between metal and NF3 involves s donation from NF3's HOMO to the empty metal d(z)(2) orbital and p back-donation from metal d(xz/yz) orbitals to NF3's LUMO, stabilizing the metal-ligand bond and destabilizing the ligand N-F bond. In FNMF2, the FN ligand is doubly bonded to the metal and has imido character.
Article
Chemistry, Physical
H. Farrokhpour, M. Gerami
Summary: This study investigates the interaction between M@Au-12 nanoclusters and different forms of cysteine mediated by the formation of Au-S bond, considering the type of core-metal (M = Au, Ag, Pd, and Pt). The adsorption energy, adsorption mode, strength of the Au-S bond, and IR spectrum of cysteine are also considered. The results suggest that the type of core-metal atoms influences the interaction between cysteine and the core-shell nanoparticles.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Inorganic & Nuclear
Kevin Parker, Geethika K. Weragoda, Alyssa Mohr, Allan J. Canty, Richard A. J. O'Hair, Victor Ryzhov
Summary: Gas-phase cationic ternary complexes of group 10 metals react with cyclohexane via C-H activation, leading to the formation of cyclohexyl species. These species undergo two competing processes: ring opening with hydrocarbon chain cracking, and dehydrogenation of the cyclohexyl ring. The prevalence of these processes is metal ion-dependent, with Pt favoring dehydrogenation over ring opening.
Article
Chemistry, Multidisciplinary
Nikolay G. Chernorukov, Oxana Nipruk, Kseniya A. Klinshova, Olga N. Tumaeva, Dmitry Sokolov
Summary: A series of new uranium compounds were synthesized and their crystal structure, solubility, and chemical stability were studied. Experimental determinations of stability and solubility of the compounds in aqueous solutions were carried out, and hydrolysis products were characterized using XRD and chemical analysis. The study is significant for assessing the long-term behavior of uranium in the environment and under repository disposal conditions.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Ahmad Najafidoust, Bahman Abdollahi, Ebrahim Abbasi Asi, Roya Karimi
Summary: Novel (Pt-Pd)@ZnO/UiO-66 nanomaterials were synthesized and the effect of different dopants, such as Ni, Pd, Pt, and mix Pt-Pd, on the photocatalytic performance of ZnO and UiO-66 was compared. The prepared nanophotocatalysts were characterized and their performance in removing dye pollutants from aqueous solutions under solar light-driven was evaluated. Results showed that doping with Pt and Pd improved the morphology and light absorption capability of the photocatalyst. Furthermore, the impact of contaminant type and initial pH solution was investigated, and the reusability and durability of the optimized sample were assessed.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Bo Jin, Rui Sun, Bin Huo, Caixia Yuan, Yan-Bo Wu
Summary: The globally stable global minima M (c) B7O7+ (M = Ni, Pd, Pt) exhibit interesting sigma-aromaticity only within the B7M core moiety, attributed to strong peripheral localized O->B pi back-bonding.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Haru Hirai, Shinjiro Takano, Takuya Nakashima, Takeshi Iwasa, Tetsuya Taketsugu, Tatsuya Tsukuda
Summary: In this study, a series of MAu12(dppe)(5)Cl-2 compounds with icosahedral structures were synthesized and their electronic structures, photoluminescence, and photocatalytic properties were systematically investigated. Doping an M element at the lower left of the periodic table expanded the energy gap between HOMO and LUMO, resulting in enhanced photoluminescence quantum yield. MAu12 (M=Pt, Rh, or Ir) exhibited higher photocatalytic activity than Au-13.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Jeongmin Cha, Eunsung Lee, Dmitry V. Yandulov
Summary: The present study describes a Pd-mediated reaction that reduces molecular oxygen to water, which can be used for oxidative transformation of organic substrates and renewable energy systems. The study reveals the autocatalytic nature of the reaction and identifies the intermediate involved in the process.
INORGANIC CHEMISTRY
(2022)
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
Biochemistry & Molecular Biology
Filip Sagan, Mariusz Mitoraj, Miroslaw Jablonski
Summary: In this study, the nature of beryllium-, magnesium-, and zinc-carbene bonds in cyclopropenylideneMIDLINE HORIZONTAL ELLIPSISMX2 (M = Be, Mg, Zn; X = H, Br) and imidazol-2-ylideneMIDLINE HORIZONTAL ELLIPSISMBr2 dimers is investigated. Various methods are used to study the bond strengths and components, showing that the CMIDLINE HORIZONTAL ELLIPSISM bond strengthens in the order of Zn < Mg << Be. Electrostatics is found to be the dominant bond component, and the σ-carbene & RARR;MX2 donation is more important than the MX2 & RARR; carbene back-donation. Substituting hydrogen atoms with bromine strengthens the metal-carbene bond in all cases. The ETS-NOCV approach uncovers the physical origin of rotational barriers.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Biochemistry & Molecular Biology
Li-Xia Bai, Jin-Chang Guo
Summary: We reported ternary MAl6S6 (M = Ni, Pd, Pt) clusters with planar hexacoordinate metal (phM) centers, which deviate from the classic 18-valence-electron rule with 16 valence electrons. These clusters were identified through unbiased global searches and confirmed by PBE0 and single-point CCSD(T) calculations. The phM MAl6 units are stabilized by peripheral bridging S atoms, and the bonding analysis reveals the existence of 10 delocalized electrons around the phM center, leading to aromaticity according to the (4n + 2) Huckel rule. It is worth noting that adding an (or two) electron(s) to its pi-type lowest unoccupied molecular orbital (LUMO) will render the system unstable.
Article
Materials Science, Multidisciplinary
Shaoce Zhang, Dong Chen, Ying Guo, Rong Zhang, Yuwei Zhao, Zhaodong Huang, Jun Fan, Johnny C. Ho, Chunyi Zhi
Summary: This study introduces the piezoelectric effect of electron-rich BaTiO3 with oxygen vacancies to enhance the performance of electrochemical nitrate reduction reaction (NO3RR). By combining with metal particles (Ru, Pd and Pt), the catalyst achieves a maximal Faradaic efficiency of 95.3% and NH3 yield rate of 6.87 mg h(-1) mg(cat)(-1). The piezoelectricity modulates the interface between metal nanoparticles and BaTiO3, enabling unobstructed electron transfer and abundant hydrogen radical production. This process suppresses the competitive hydrogen evolution reaction (HER) and promotes the hydrogenation of reaction intermediates in NO3RR.
Article
Chemistry, Physical
Zahra Rajabi, Michela Martinelli, Caleb D. Watson, Donald C. Cronauer, A. Jeremy Kropf, Gary Jacobs
Summary: In the investigation of low temperature water-gas shift (LTS) reaction, it was found that increasing the loading of lithium dopant can enhance the reaction rate, but high levels of lithium loading can suppress the hydrogen transfer capacity required by platinum site and increase the catalyst basicity. Electron transfer is unlikely the main cause of C-H bond weakening in formate.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Review
Biochemistry & Molecular Biology
Adriana Coricello, James D. Adams, Eric J. Lien, Christopher Nguyen, Filomena Perri, Travis J. Williams, Francesca Aiello
CURRENT MEDICINAL CHEMISTRY
(2020)
Article
Chemistry, Physical
Valeriy Cherepakhin, Travis J. Williams
Article
Polymer Science
Yijia Ma, Carlos A. Navarro, Travis J. Williams, Steven R. Nutt
POLYMER DEGRADATION AND STABILITY
(2020)
Review
Chemistry, Organic
Valeriy Cherepakhin, Travis J. Williams
Summary: This review highlights the importance of oxidizing primary alcohols to carboxylic acids and the use of transition-metal compounds as catalysts, emphasizing their atom economy and green chemistry principles, making it suitable for a modern survey.
SYNTHESIS-STUTTGART
(2021)
Article
Engineering, Environmental
Euna Kim, Georgia B. Cardosa, Katarina E. Stanley, Travis J. Williams, Daniel L. McCurry
Summary: Water reuse is expanding due to water scarcity, but recent research has found that low-molecular-weight aldehydes still make up a significant fraction of recycled wastewater in certain treatment configurations.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Chris Rabot, Yuhao Chen, Swati Bijlani, Yi-Ming Chiang, C. Elizabeth Oakley, Berl R. Oakley, Travis J. Williams, Clay C. C. Wang
Summary: This article presents a novel chemical and biological approach for the rapid conversion of polyethylenes into structurally complex and pharmacologically active compounds. By engineering strains of the fungus Aspergillus nidulans, the authors have produced fungal secondary metabolites from the digestion products of polyethylenes, expanding the range of products to which polyethylenes can be upcycled.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Clay C. C. Wang, Travis J. Williams, Chris Rabot, Yuhao Chen, Shu-Yi Lin, Ben Miller, Yi-Ming Chiang, C. Elizabeth Oakley, Berl R. Oakley
Summary: Polystyrene (PS) is a commonly used plastic that is not frequently recycled. In this study, a scalable process was developed to convert PS into benzoic acid, which can then be biosynthetically upgraded into various secondary metabolites by engineered strains of the fungus Aspergillus nidulans. This approach expands the range of plastic-derived products and demonstrates the potential for utilizing PS waste in the production of valuable compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Anju Nalikezhathu, Adriane Tam, Valeriy Cherepakhin, Van K. Do, Travis J. Williams
Summary: We present a method for synthesizing 1,4-diazacycles via diol-diamine coupling using a (pyridyl)phosphine-ligated ruthenium(II) catalyst (1), which is unique to this study. The reaction can proceed through either two sequential N-alkylations or an intermediate tautomerization pathway to yield piperazines and diazepanes, with diazepanes typically inaccessible through catalytic routes. Our conditions are compatible with various amines and alcohols commonly used in the synthesis of important medicinal compounds. We demonstrate the synthesis of cyclizine and homochlorcyclizine with yields of 91% and 67%, respectively.
Article
Chemistry, Multidisciplinary
Zehan Yu, Y. Justin Lim, Travis Williams, Steven Nutt
Summary: We propose an electrochemical process to recycle carbon fiber (CF) fabrics from amine-epoxy carbon fiber-reinforced polymers (CFRPs). By using a Kolbe-like mechanism, methyl radicals are generated from CH3COOH to break C-N bonds within epoxy matrices through hydrogen atom abstraction. The recovered CFs can be directly remanufactured into CFRPs without resizing.
Article
Chemistry, Multidisciplinary
Long Zhang, Zhiyao Lu, Andrew R. Rander, Travis J. Williams
Summary: We present two bifunctional (pyridyl)carbene-iridium(i) complexes capable of catalyzing the hydrogenation of ketones and aldehydes at ambient pressure. Various aryl, heteroaryl, and alkyl groups are successfully hydrogenated, and mechanistic studies uncover a unique polarization effect in which the rate depends on proton transfer rather than hydride transfer. This method offers a convenient and waste-free alternative to traditional borohydride and aluminum hydride reagents.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Van K. Do, Nicolas Alfonso Vargas, Anthony J. Chavez, Long Zhang, Valeriy Cherepakhin, Zhiyao Lu, Robert P. Currier, Pavel A. Dub, John C. Gordon, Travis J. Williams
Summary: This study demonstrates that homogenous catalysts with different ligand frameworks are suitable for dehydrogenation of neat formic acid under self-pressurizing conditions, and their performance differences can be related to structural differences. The important roles of H-2 and CO in catalyst activation and speciation are also revealed.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Kristopher M. Koskela, Stephen J. Quiton, Shaama Mallikarjun Sharada, Travis J. Williams, Richard L. Brutchey
Summary: This study demonstrates the facile dissolution of zinc oxide using a binary alkahest system. The dissolution mechanism involves the binding of thiols to the zinc oxide surface, followed by the addition of other ligands and cleavage of the zinc complex. The insights gained from this study can inform the dissolution of other bulk oxides into inks for solution processed thin films.
Article
Chemistry, Multidisciplinary
Carlos A. Navarro, Yijia Ma, Katelyn H. Michael, Hanna M. Breunig, Steven R. Nutt, Travis J. Williams
Summary: The presented catalytic, aerobic conditions enable depolymerization of amine-linked epoxy thermoset matrix polymers commonly found in high-performance CFRP materials. Unlike other recycling methods, this process retains the aligned and woven fibers in the same pattern as the parent material and recovers valuable materials from the thermoset matrix.
Review
Chemistry, Physical
Nicolas Alfonso, Van K. Do, Anthony J. Chavez, Yuhao Chen, Travis J. Williams
Summary: The proliferation of increasingly useful hydrogen transfer reactions in organic synthesis has introduced many new homogeneous catalysts. Unlike traditional cross-coupling reactions, these emerging hydrogen transfer catalysts exhibit a rich diversity in mechanisms for activation, speciation, C-H bond cleavage and formation.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Sara R. Smock, Katayoon Tabatabaei, Travis J. Williams, Susan M. Kauzlarich, Richard L. Brutchey
