Article
Chemistry, Multidisciplinary
Wenwen Lin, Hao Chen, Gaobo Lin, Siyu Yao, Zihao Zhang, Jizhen Qi, Meizan Jing, Weiyu Song, Jing Li, Xi Liu, Jie Fu, Sheng Dai
Summary: In this study, a defective boron carbon nitride catalyst was developed, which achieved high Faraday efficiency and ammonia yield, and had long-term durability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Aya Eizawa, Kazuya Arashiba, Hiromasa Tanaka, Asuka Konomi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: In this study, dimolybdenum complexes with quaterphenylene-bridged PNP-type pincer ligands were designed and synthesized based on DFT calculations. The results showed that these complexes exhibited excellent catalytic activity for the synthesis of ammonia from dinitrogen under ambient conditions using samarium diiodide as a reductant and water as a proton source.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Aya Eizawa, Kazuya Arashiba, Hiromasa Tanaka, Asuka Konomi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: Dimolybdenum complexes bearing 3,3'''-(1,1':3',1'':3'',1'''-quaterphenylene)-bridged pyridine-based PNP-type pincer ligand were designed and prepared based on DFT calculations. These complexes serve as effective catalysts for the conversion of dinitrogen to ammonia under ambient reaction conditions, using samarium diiodide as a reductant and water as a proton source.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Quinton J. Bruch, Santanu Malakar, Alan S. Goldman, Alexander J. M. Miller
Summary: This study demonstrates the electrochemical N-2 binding and splitting capabilities of a molybdenum complex, and investigates the reaction pathways and intermediates involved. Electrochemical kinetic analysis, spectroelectrochemical monitoring, and computational studies reveal two concurrent reaction pathways.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Honghao Chu, Shisheng Zheng, Yang Li, Kuanda Xu, Qingshui Hong, Tangyi Li, Wenju Ren, Shunning Li, Zongwei Mei, Feng Pan
Summary: By tuning the exposure of BiVO4 {010} facets, enhanced N-2 photofixation performance has been achieved for the first time.
Article
Chemistry, Multidisciplinary
Gao-Xiang Wang, Xueli Wang, Yang Jiang, Wang Chen, Chunxiao Shan, Peng Zhang, Junnian Wei, Shengfa Ye, Zhenfeng Xi
Summary: Electrophilic functionalization of N2 moieties in metal dinitrogen complexes is challenging, and efficient conversion of N2 into diazenido and hydrazido species is still a great obstacle. In this study, we provide a detailed investigation on the reaction intricacies, revealing fleeting diazenido intermediates and long-lived hydrazido products. Both the first and second electrophilic functionalization steps show quantitative conversions at low temperatures. Based on these findings, large-scale and near-quantitative preparation of all hydrazido species is achieved.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Chenshu Dai, Yuanyuan Huang, Jun Zhu
Summary: This study discusses the challenge of activating dinitrogen (N-2) under mild conditions and introduces the potential of using carborane derivatives for N-2 activation. Through theoretical calculations, it is found that carborane-based frustrated Lewis pairs (FLPs) have low reaction barriers and high exothermicity for N-2 activation, indicating the potential for metal-free N2 activation under mild conditions.
Article
Chemistry, Multidisciplinary
Fushan Wen, Xiaoli Huang, Yajie Li, Le Pang, Yuan Xu, Tao Zhang
Summary: Photocatalytic nitrogen fixation using a pinecone-shaped graphite-phase carbon nitride (PCN) catalyst supported with MoS2 nanosheets was designed and studied. The catalyst exhibited excellent performance in the photocatalytic nitrogen reduction reaction (PNRR) due to its large specific surface area and enhanced visible light absorption. The PCN loaded with 5 wt % MoS2 nanosheets (MS5%/PCN) showed a PNRR efficiency of 279.41 μmol g(-1) h(-1), which was significantly higher than other catalysts tested. The unique pinecone-like structure of MS5%/PCN improved light absorption and facilitated uniform loading of MoS2 nanosheets. The presence of MoS2 nanosheets also enhanced light absorption ability and reduced impedance, while efficiently adsorbing and reducing nitrogen (N2).
Article
Engineering, Environmental
Fengfeng Wang, Qijia Ding, Jinrui Ding, Yajie Bai, Hongye Bai, Weiqiang Fan
Summary: This study introduces a ZnIn2S4/BiVO4 heterostructure with zinc vacancies for efficient chemisorption and catalytic kinetics of nitrate reduction. The formation of frustrated Lewis pairs plays a critical role in enhancing the selectivity and yield rate. These findings expand the prospect of using frustrated Lewis pairs as active sites in photoelectrochemical nitrate reduction reactions.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Xiaoyu Liang, Xinkui Wang, Xinxin Zhang, Sisi Lin, Min Ji, Min Wang
Summary: In this study, a ZnIn2S4/In(OH)3-x (ZIOS) heterojunction was developed for visible-light-driven CO2 reduction. The ZIOS composites, fabricated via partial sulfurization of Zn-In-O oxide, exhibit a CO formation rate of 1945.5 mu mol center dot g-1 center dot h-1, which is about 2.76-fold higher than that over ZnIn2S4, and suppress hydrogen evolution, with the CO/H2 ratio increasing from 0.436 for ZnIn2S4 to 1.6 for ZIOS. This work provides insight into the design of efficient CO2 reduction photocatalysts.
Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Weining Zhang, Zhenhua Yang, Hailian Wang, Lei Lu, Depei Liu, Taozhu Li, Shicheng Yan, Hao Qin, Tao Yu, Zhigang Zou
Summary: Research shows that FLPs with shorter acid-base distance are more efficient in CO2 activation. The combination effects between facet junction separating charges and FLPs activating molecules can accelerate CO2 reduction.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Ting Wang, Qian Liu, Tingshuai Li, Siyu Lu, Guang Chen, Xifeng Shi, Abdullah M. Asiri, Yonglan Luo, Dongwei Ma, Xuping Sun
Summary: This study reports that a Mo3Si thin film sputtered on graphite paper is a favorable electrocatalyst for NH3 synthesis under ambient conditions, with high NH3 yield rate and Faraday efficiency. The synergy of metallic conductivity of Mo3Si and high chemical activity of exposed Mo ions benefits the adsorption and activation of N-2, leading to NH3 production.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Chemistry, Physical
Ting Wang, Qian Liu, Tingshuai Li, Siyu Lu, Guang Chen, Xifeng Shi, Abdullah M. Asiri, Yonglan Luo, Dongwei Ma, Xuping Sun
Summary: This study reports the electrocatalytic properties of a Mo3Si thin film sputtered on graphite paper for NH3 synthesis, showing high NH3 yield rate and Faraday efficiency, as well as demonstrating excellent stability and selectivity. The synergy of metallic conductivity of Mo3Si and high chemical activity of exposed Mo ions benefits N-2 adsorption and activation, ultimately leading to NH3 production.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Guoqiang Zhang, Tanggao Liu, Jinyi Song, Yingyu Quan, Li Jin, Mengyue Si, Qian Liao
Summary: In this study, a new method for converting N-2 into iminophosphorane was reported, and N-containing organophosphine compounds were successfully synthesized under mild conditions. The efficient cleavage and transformation of N-2 were achieved by visible light irradiation and specific ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Josef T. Boronski, Laurence R. Doyle, John A. Seed, Ashley J. Wooles, Stephen T. Liddle
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Samantha K. Furfari, Bengt E. Tegner, Arron L. Burnage, Laurence R. Doyle, Alexander J. Bukvic, Stuart A. Macgregor, Andrew S. Weller
Summary: Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques were used to synthesize and characterize a sigma-alkane complex with different alkane binding modes. The comparison, supported by analysis, reveals that the different regioselectivity is related to subtle changes in the local microenvironment surrounding the alkane ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jingzhen Du, David Hunger, John A. Seed, Jonathan D. Cryer, David M. King, Ashley J. Wooles, Joris van Slageren, Stephen T. Liddle
Summary: This study reports the synthesis of a uranium diphosphorus complex with a unique structure and reactivity through a P atom transfer approach. Experimental and computational characterization reveal the activation of the diphosphorus ligand and the presence of distinctive U-P bonding interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Benjamin L. L. Reant, Victoria E. J. Berryman, Annabel R. Basford, Lydia E. Nodaraki, Ashley J. Wooles, Floriana Tuna, Nikolas Kaltsoyannis, David P. Mills, Stephen T. Liddle
Summary: In this study, Si-29 NMR spectroscopy and DFT calculations were combined to investigate the covalency in the chemical bonding of s- and f-block metal-silicon bonds. The results showed a wide range of metal-bound Si-29 NMR isotropic chemical shifts and linear correlations between dSi and computed delocalization indices. The calculations revealed dominant s- and d-orbital character in the bonding of these silanide complexes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Laurence R. Doyle, Emily A. Thompson, Arron L. Burnage, Adrian C. Whitwood, Huw T. Jenkins, Stuart A. Macgregor, Andrew S. Weller
Summary: The study found that the [S-BAr4F](-) anion enhances the stability of the sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BAr4F] both thermally and when suspended in pentane. Furthermore, the increased stability of [S-BAr4F](-) salts is mainly attributed to enhanced non-covalent interactions in the lattice.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Michal S. Dutkiewicz, Conrad A. P. Goodwin, Mauro Perfetti, Andrew J. Gaunt, Jean-Christophe Griveau, Eric Colineau, Attila Kovacs, Ashley J. Wooles, Roberto Caciuffo, Olaf Walter, Stephen T. Liddle
Summary: Neptunium, the first artificially synthesized actinide, has been less studied compared to its famous neighbors uranium and plutonium. This study reports the synthesis, isolation, and characterization of a stable molecular neptunium(V)-mono(oxo) triamidoamine complex, demonstrating the possibility of stabilizing and studying high-oxidation-state transuranic complexes with a single metal-ligand bond.
Article
Chemistry, Inorganic & Nuclear
Laurence R. Doyle, Martin R. Galpin, Samantha K. Furfari, Bengt E. Tegner, Antonio J. Martinez-Martinez, Adrian C. Whitwood, Scott A. Hicks, Guy C. Lloyd-Jones, Stuart A. Macgregor, Andrew S. Weller
Summary: The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] with H2 or D2 was studied using solid-state NMR spectroscopy and solution quenching techniques. The quantification of the reaction was done using a two-step JMAK model, revealing an inverse isotope effect for the second addition of H2 and the possibility of obtaining the structural solution of the alkane complex using D2. The results were supported by periodic DFT calculations.
Article
Chemistry, Multidisciplinary
Conrad A. P. Goodwin, Ashley J. Wooles, Jesse Murillo, Erli Lu, Josef T. Boronski, Brian L. Scott, Andrew J. Gaunt, Stephen T. Liddle
Summary: The synthesis and characterization of transuranium-carbene derivatives have been reported, exploring their bond interactions and reactivity. Computational analysis reveals the covalent nature of NpIII=C bonds and provides comparisons with other congeners.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Letter
Multidisciplinary Sciences
Josef T. Boronski, John A. Seed, David Hunger, Adam W. Woodward, Joris van Slageren, Ashley J. Wooles, Louise S. Natrajan, Nikolas Kaltsoyannis, Stephen T. Liddle
Article
Chemistry, Inorganic & Nuclear
John A. Seed, Lisa Vondung, Ralph W. Adams, Ashley J. Wooles, Erli Lu, Stephen T. Liddle
Summary: This study reports the synthesis and characterization of uranium and thorium mesoionic carbene complexes and reveals the varying nature of actinide-MIC bonding as a function of actinide oxidation state. Through experimental and computational analysis, the stability differences between the two complexes and the equilibrium state in solution were revealed.
Article
Chemistry, Multidisciplinary
Jingzhen Du, Gabor Balazs, John A. Seed, Jonathan D. Cryer, Ashley J. Wooles, Manfred Scheer, Stephen T. Liddle
Summary: The study reports the direct synthesis of terminal pnictidenes and their conversion to pnictides, highlighting the importance of the super-bulky Tren(TCHS) ligand. The findings provide valuable insights into thorium-arsenic bonding.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Stephen T. . Liddle, David P. Mills, Benjamin L. L. Reant, Ashley J. Wooles
Summary: The salt metathesis reactions of the yttrium methane-diide iodide complex [Y(BIPM)(I)(THF)2] with the group 1 silanide ligand-transfer reagents MSiR3 (M = Na, R3 = tBu2Me or tBu3; M = K, R3 = (SiMe3)3) yielded the yttrium methanediide silanide complexes [Y(BIPM)(SitBu2Me)(THF)] (1), [Y(BIPM)(SitBu3)(THF)] (2), and [Y(BIPM){Si(SiMe3)3}-(THF)] (3). These complexes provide rare examples of structurally authenticated rare earth metal-silicon bonds and were characterized by various spectroscopic techniques. Density functional theory calculations revealed the predominantly ionic Y-Si bonding in 1-3. Reactivity studies showed the preferential 1,2-migratory insertion of unsaturated substrate into the Y-Si bond, as well as [2+2] cycloaddition reaction at the Y=C bond with certain substrates.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Gemma K. Gransbury, Benjamin L. L. Reant, Ashley J. Wooles, Jack Emerson-King, Nicholas F. Chilton, Stephen T. Liddle, David P. Mills
Summary: In this study, the synthesis of U(III) bis(cyclopentadienyl) hypersilanide complex was reported, and isostructural lanthanide and group 4 M(III) homologues were synthesized for comparison of metal-silicon bonding between early d- and f-block metals. The complexes were characterized using various spectroscopic techniques, crystallography, magnetometry, elemental analysis and ab initio calculations. The results showed that the anisotropy axis in the d-block complexes is governed by the hypersilanide ligand, while in the f-block congeners it is fixed by the two Cp '' ligands. It was also found that the covalency in these complexes follows the order Zr > Ti >> U > Nd ≈ Ce ≈ La, with uranium showing greater covalency compared to neodymium. The bonding interactions were analyzed using EPR, electronic absorption spectra, magnetic measurements and calculations.
Article
Chemistry, Inorganic & Nuclear
Benjamin L. L. Reant, Dukula De Alwis Jayasinghe, Ashley J. Wooles, Stephen T. Liddle, David P. Mills
Summary: We synthesized and characterized a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the formula [M(Cp-R)(2){Si(SiMe3)(3)}(X)]. The reactions of [M(Cp-R)(2)(Cl)(2)] with K{Si(SiMe3)(3)} gave mono-silanide complexes [M(Cp')(2){Si(SiMe3)(3)}(Cl)]. The complexes were characterized by XRD, NMR spectroscopy, ATR-IR spectroscopy, and density functional theory calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Josef T. Boronski, John A. Seed, Ashley J. Wooles, Stephen T. Liddle
Summary: In this study, a room temperature reaction between a uranium-carbene complex and white phosphorous was conducted to form an organophosphorus compound. This reaction demonstrated cooperative metal-carbene and P-4 activation, producing different compounds when carried out at low temperature. The findings provide insights into direct fragmentation, catenation, and functionalization of P-4, showcasing a novel synthetic cycle.
CHEMICAL COMMUNICATIONS
(2021)