Article
Chemistry, Organic
Hanyang Bao, Limeng Zheng, Qian Liu, Mingfeng Han, Ya Li, Miao Bao, Yuanqiang Li, Pucha Yan, Yunkui Liu
Summary: A synthetic idea for the efficient utilization of α-chiral alkyl aldehydes as deoxygenative chiral alkyl radical equivalents has been proposed and applied successfully. This strategy is based on a photocatalytic traceless C-N bond formation/cleavage and catalyzed by 4-CzIPN. Under mild reaction conditions, 6-alkyl-substituted phenanthridines are obtained through alkylation/cyclization of 2-biphenylisonitriles with α-chiral alkyl aldehydes in the presence of amines. In most cases, the optical purity of the chiral centers inherited from the corresponding mother aldehyde is preserved.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
David T. Nemoto Jr, Kang-Jie Bian, Shih-Chieh Kao, Julian G. West
Summary: The place of alkyl radicals in organic chemistry has evolved from challenging uncontrollable species to versatile intermediates enabling construction of various bonds. This evolution has been facilitated by advances in radical generation and functionalization methods, including hydrogen atom transfer and radical-polar crossover. Among these methods, radical ligand transfer (RLT) has emerged as a promising means of catalytically forming new bonds to alkyl radicals. RLT catalysis offers the ability to form diverse bonds using earth abundant element catalysts and is compatible with various radical generation methods.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xian-Guan Liu, Ci-Shuang Dong, Fei Li, Bo Zhang
Summary: The study presents a manganese-mediated strategy for direct functionalization of Hantzsch esters with alkyl iodides, leading to the synthesis of valuable 4-alkyl-1,4-dihydropyridines. This practical reaction, operating under visible-light irradiation at room temperature, shows high functional-group compatibility and is suitable for gram-scale synthesis and late-stage functionalization.
Article
Chemistry, Inorganic & Nuclear
Ya-Nan Zhao, Changhai Liu, Siqi Xu, Shengkang Min, Wenchang Wang, Naotoshi Mitsuzaki, Zhidong Chen
Summary: In this paper, Pr0.7Sr0.3Co1-xRu x O3 perovskite oxides were synthesized by the sol-gel method as bifunctional catalysts for HER and OER. The PSCR0.05 catalyst showed low overpotentials and high durability for both HER and OER in alkaline medium. The electrocatalytic performance was further improved by introducing A- and B-site cationic doping regulation, which increased the surface oxygen vacancy and active site.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
D. O. Khristolyubov, D. M. Lyubov, A. A. Trifonov
Summary: The review discusses the synthesis, structure, reactivity, and catalytic activity of alkyl derivatives of rare earth metals in the +2 oxidation state (Sm, Eu, Yb) and their analogues containing heavy alkaline earth metals (Ca, Sr, Ba), highlighting the unique features of these compounds with highly reactive M7C bonds. The bibliography includes 157 references.
RUSSIAN CHEMICAL REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Dawei Li, Lichao Ning, Qiliang Luo, Shiyu Wang, Xiaoming Feng, Shunxi Dong
Summary: An array of rare-earth bis(aminobenzyl) complexes supported by imidazolin-2-iminato ligands were synthesized and characterized. These complexes displayed high reactivity towards ortho-Csp(2)-H alkylation of 2-alkylpyridines and benzylic Csp(3)-H alkylation of 2,6-dialkylpyridines with alkenes, providing an atom-economical approach to alkylated pyridine derivatives. Mechanistic investigations revealed the catalytic cycle and enantioselectivity in the asymmetric version of Csp(3)-H alkylation.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shin-Ho Kim-Lee, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: A novel dual Cu catalysis strategy based on a dynamic multiligand coordination pool is described, triggering cooperative polar/radical pathways in a single catalytic cycle. This strategy overcomes the reactivity issue in Cu-catalyzed carboboration, expanding the scope of the reaction and opening avenues to access stereodefined tetrasubstituted vinylboronates.
Article
Chemistry, Inorganic & Nuclear
Benjamin E. Fener, Philipp Schueler, Helmar Goerls, Phil Liebing, Matthias Westerhausen
Summary: The alkaline-earth metalation of dimesitylphosphane oxide Mes(2)P(O)H in ethereal solvents with dialkylmagnesium and alkylmagnesium bromide, as well as the homoleptic bis(trimethylsilyl)amides of calcium, strontium, and barium, produces various complexes depending on the stoichiometry. The exchange of ligands in one of the complexes allows the isolation of different compounds. In ethereal solutions, the heteroleptic complexes undergo Schlenk-type equilibria, interconverting into their homoleptic counterparts.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Multidisciplinary
Yu-qian Liu, Meng-hui Wang, Bing Yan, Lu Li, Sudip Pan, Zhong-hua Cui, Gernot Frenking
Summary: This study reports the quantum chemical calculations of the diatomic molecules AeB(-) and AeC (Ae=Ca, Sr, Ba). The results show that AeB(-) has an electronic triplet ((3)sigma(-)) ground state, while AeC has a lower-lying triplet state. The bonding in AeC is stronger compared to AeB(-).
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Nils Kretzschmar, Oliver Busse, Maria Roslova, Martin Hantusch, Markus Seifert
Summary: This study investigates the effect of alkaline promoters on Ni-based catalysts for the selective hydrodeoxygenation of lignin surrogate guaiacol. The use of alkaline oxides leads to preferred demethoxylation and accumulation on nickel corners, resulting in higher conversion and selectivity for KA-oil. The operating parameters were optimized using design of experiments, and the Ni-CaO/SiO2 catalyst showed the most promising results for caprolactam synthesis.
Article
Engineering, Environmental
Jiashu Huang, Xiaoshan Zheng, Yang Liu, Fengliang Wang, Daguang Li, Haijin Liu, Ruobai Li, Tiansheng Chen, Wenying Lv, Guoguang Liu
Summary: In this study, a facile strategy was introduced for the creation of oxygen vacancies in BiOI via Sr2+ doping, leading to significantly enhanced photocatalytic degradation of indometacin under visible light exposure. The improved performance was attributed to the accelerated separation of charge carriers by oxygen vacancies and electron trapping by Sr ions. The study provides new insights for the synthesis of efficient and cost-effective BiOI-based photocatalysts and offers a promising strategy for advanced environmental remediation.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Chemistry, Physical
Peter Drabo, Matthias Fischer, Valerie Toussaint, Franziska Flecken, Regina Palkovits, Irina Delidovich
Summary: The isomerization of D-glucose into D-fructose in the presence of different metal (hydro)oxides as catalysts involves homogeneous catalysis by released hydroxide ions, with magnesium oxide being a stable generator of OH- during the reaction. Although various metal (hydro)oxides induce alkalinity differently, they all exhibit similar conversion-selectivity patterns, indicating a common catalytically active species OH-. The use of filtration and contact tests for estimating contributions of homogeneous and heterogeneous catalysis is comprehensively evaluated, noting potential deceptive results from the in situ generation of hydroxide ions during base-catalyzed isomerization.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Applied
Shubhajit Das, Bart De Tobel, Mercedes Alonso, Clemence Corminboeuf
Summary: Advances in alkaline earth metal hydrogenation catalysis have expanded the potential catalytic options, with focus on the impact of metal-ligand combinations on catalytic activity. The charge and size of metal ions are the major factors determining catalytic activity, while ligands play a minor role. Volcano plots can be used for rapid screening of prospective Ae catalysts to achieve maximum activity in hydrogenation processes.
TOPICS IN CATALYSIS
(2022)
Article
Engineering, Environmental
Xuejing Xiao, Ruixue Guo, Yumeng Qi, Junyan Wei, Nannan Wu, Shengnan Zhang, Ruijuan Qu
Summary: TiO2 nanospheres prepared by the sol-gel method were found to efficiently catalyze the photo-degradation of 1-butyl-2,3-dimethylimidazolium bromide salt ([BMMIm]Br) under simulated solar irradiation through the main attack of hydroxyl radicals ( OH). The introduction of alkali and alkaline earth metal ions enhanced the formation of OH, leading to increased degradation efficiency. The removal efficiency of [BMMIm](+) remained high in real waters. Different reactions, such as hydroxyl substitution, bond breaking, direct oxidation, and ring opening, were observed during the photocatalytic degradation process.
JOURNAL OF HAZARDOUS MATERIALS
(2024)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Emma Richards
Summary: Ionic compounds containing sodium cations are known for their stability and resistance to redox reactivity. However, when treated with non-reducible organic bases, a low oxidation state {Mg2Na2} species undergoes selective extrusion of sodium metal and oxidation of the Mg-I centers. Quantum chemical studies indicate that intramolecular electron transfer is facilitated by the molecular orbitals of the {Mg2Na2} ensemble.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Laura E. English, Thomas M. Horsley Downie, Catherine L. Lyall, Mary F. Mahon, Claire L. McMullin, Samuel E. Neale, Carla M. Saunders, David J. Liptrot
Summary: The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane resulted in the formation of boraformamides, pinBN(R)C(O)H, in most cases. Overreduction was observed only for electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis revealed that the stability of [(IPr)CuH](2), proposed as the catalyst resting state, influences selectivity and offers a potential solution to prevent overreduction in future work. In the case of iPrNCO, the formation of [(IPr)CuH](2) prevents overreduction kinetically. However, for 4-NC-C6H4NCO, the barrier height for the first step of overreduction is much lower, resulting in unselective reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kyle G. G. Pearce, Michael S. S. Hill, Mary F. F. Mahon
Summary: Reaction of BeCl2 with dilithium diamide yields the dimeric chloroberyllate, leading to the formation of a 2-coordinate beryllium amide. Reduction of the beryllium amide using lithium or sodium in benzene produces relevant organoberyllate products, likely through transient Be(i) radicals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Erika M. Roberts, Fedor M. Miloserdov, Victor Varela-Izquierdo, Mary F. Mahon, Michael K. Whittlesey
Summary: The addition of excess ZnMe2 to a mixture of [Ru(PPh3)(3)HCl] and IMes resulted in the formation of a bis-cyclometallated complex [Ru(IMes)(PPh3)(2)] 2 and a mono-cyclometallated Ru-Zn heterobimetallic complex [Ru(IMes)'(PPh3)(2)(ZnMe)] 3. Further reactions of these complexes with H-2, PhSiH3, pinacolborane, and CO were investigated. Compounds 1, 4, 5, and 6 were synthesized and structurally characterized.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Devyani Srivastava, Amita Singh, Gabriele Kociok-Kohn, Om Prakash, Abhinav Kumar, Mohd. Muddassir
Summary: This report presents two sulfido-bridged trinuclear Ni(II) clusters and characterizes them using X-ray crystallography. The non-covalent interactions and Ni dot dot dot Ni interactions in these compounds are analyzed using Hirshfeld surface analysis, density functional theory, and quantum theory of atoms-in-molecules.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Antoine Buchard, Matthew G. Davidson, Gerrit Gobius du Sart, Matthew D. Jones, Gabriele Kociok-Kohn, Strachan N. Mccormick, Paul Mckeown
Summary: We have reported three niobium-based initiators for the catalytic ring-opening polymerization (ROP) of epsilon-caprolactone, exhibiting good activity and molecular weight control. Among them, a monometallic cationic alkoxo-Nb(V) epsilon-caprolactone adduct has been prepared on the gram-scale and characterized, which represents an unprecedented example of a metal complex with an intact lactone monomer and a functional ROP-initiating group simultaneously coordinated at the metal center. At 80 degrees C, all three systems initiate the immortal solution-state ROP of epsilon-caprolactone via a coordination-insertion mechanism, which has been confirmed through experimental studies, and is supported by computational data. Natural bond orbital calculations further indicate that polymerization may necessitate isomerization about the metal center between the alkoxide chain and the coordinated monomer. The observations made in this work are expected to inform mechanistic understanding both of amine tris(phenolate)-supported metal alkoxide ROP initiators, including various highly stereoselective systems for the polymerization of lactides and of coordination-insertion-type ROP protocols more broadly.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hugh J. Sanderson, Gabriele Kociok-Kohn, Ulrich Hintermair
Summary: The first magnesium pentalenide complexes were synthesized via deprotonative metalation, and their structure and reactivity were studied. The electronic influence of the aryl substituents on the pentalenide core resulted in electrophilic addition at 1,5-positions instead of 1,4-positions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jodie L. Hann, Catherine L. Lyall, Gabriele Kociok-Kohn, Simon E. Lewis
Summary: This study presents a method for the synthesis of N-alkoxycarbonyl pyrroles by the condensation of readily available O-substituted carbamates with 2,5-dimethoxytetrahydrofuran. It is demonstrated that N-alkoxycarbonyl protection can impart distinct reactivity to pyrrole in comparison with N-sulfonyl protection.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Rosalyn L. Falconer, Esme Owen, Michael J. Cowley, John P. Lowe, Claire L. McMullin, Mary F. Mahon, Michael K. Whittlesey
Summary: Treatment of [Ru(L)(PPh3)2(CO)H2] (L = PPh3, IMes) with an N-mesityl amidophosphine aluminium dihydride complex (Al(P-N)H2) gives [Ru(PPh3)2(CO)H3{Al(P-N)H}] (2) and [Ru(IMes)(PPh3)(CO)H3{Al(P-N)H}] (4), which are present in solution as mixtures of diastereomers. Crystal structure determinations and density functional theory (DFT) calculations suggest both 2 and 4 can be formulated as [Ru(L)(PPh3)(CO)H3][Al(P-N)H] complexes with bridging hydride ligands.
Article
Chemistry, Multidisciplinary
Devyani Srivastava, Amita Singh, Gabriele Kociok-Koehn, Suresh W. Gosavi, Ratna Chauhan, Muthupandian Ashokkumar, Abhinav Kumar, Mohd. Muddassir
Summary: Three new heteroleptic Co(iii) ferrocene dithiocarbamate complexes with dppe as ligand have been synthesized and characterized. Single crystal X-ray diffraction revealed a distorted octahedral geometry around Co(iii) in the complexes. The compounds were used as photo-sensitizers in dye-sensitized solar cells and exhibited good photovoltaic performance.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chiteri Gautam, Devyani Srivastava, Gabriele Kociok-Kohn, Suresh W. Gosavi, Vinod K. Sharma, Ratna Chauhan, Dattatray J. Late, Abhinav Kumar, Mohd. Muddassir
Summary: Two Schiff base complexes, [CuL2] (Cu-Sal) and [CoL3] (Co-Sal), were synthesized and characterized. Crystal structure analysis showed a square planar geometry around Cu(ii) and various intermolecular non-covalent interactions in Cu-Sal. Both complexes were used as sensitizers in TiO2 based dye sensitized solar cells (DSSCs), and Co-Sal exhibited better photovoltaic performance than Cu-Sal due to improved light absorption and dye loading.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Benjamin L. Morrison
Summary: [{SiNDipp}MgNa](2) reacts directly with H-2 to form a heterobimetallic hydride. Computational density functional theory (DFT) studies suggest that this reactivity is initiated by orbitally-constrained sigma(Mg-Mg)-> sigma*(H-H) and sigma(H-H) -> n*(Na(3s)) interactions between the frontier MOs of both H-2 and the tetrametallic core of [{SiNDipp}MgNa](2).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.
Article
Biochemistry & Molecular Biology
Megan J. Green, Haobo Ge, Stephen E. Flower, Charareh Pourzand, Stanley W. Botchway, Hui-Chen Wang, Navaratnarajah Kuganathan, Gabriele Kociok-Kohn, Meng Li, Suying Xu, Tony D. James, Sofia I. Pascu
Summary: New design and synthetic strategies were developed to generate functional phenyl boronic acid-based fluorescent probes with a 1,8-naphthylimide bright core, and their beta-d-glucan hybrids. These were monitored by MP FLIM for their ability to report changes in their environments in live cells.
RSC CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Devyani Srivastava, Aparna Kushwaha, Gabriele Kociok-Kohn, Suresh W. Gosavi, Ratna Chauhan, Muthupandian Ashokkumar, Abhinav Kumar, Mohd. Muddassir
Summary: Three new nickel complexes were synthesized and used as sensitizers in dye sensitized solar cells (DSSCs). Among the three sensitizers, the DSSC fabricated using p-NiL exhibited the best photovoltaic performance with an efficiency of 3.40%, strong electronic coupling, and enhanced electron injection.
