Article
Multidisciplinary Sciences
Jian-Qiang Huang, Meng Yu, Xuefeng Yong, Chun-Yu Ho
Summary: The direct addition of isocyanides to cyclopropenes is challenging. Here, the authors report a catalytic cyclopropene-isocyanide [5 + 1] benzannulation catalyzed by an (N-heterocyclic carbene)Ni(II) complex; this method enables the preparation of fused and multi-substituted anilines and unsymmetrically functionalized spiro-ring structures.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Zhifeng Zhang, Yang Chen, Xiao Gu, Chun-Yu Ho
Summary: Well-controlled olefin insertion is crucial for achieving efficient and selective bulk and fine-chemical synthesis. Nickel catalysts, particularly those based on N-heterocyclic carbene (NHC) ligands, have shown great potential in meeting the diverse demands of olefin codimerization and hydrovinylation. These catalysts offer a high level of control and have the ability to unite previously unreactive substrate pairs, leading to the synthesis of complex and structurally diverse compounds.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Biochemistry & Molecular Biology
Nasir S. Lawal, Halliru Ibrahim, Muhammad D. Bala
Summary: In this study, four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes were synthesized and characterized through various spectroscopic methods. In the catalytic oxidation of styrene, these complexes exhibited good catalytic activity and high selectivity to benzaldehyde. Kinetic studies also revealed the activation energy and order of the reaction.
Article
Chemistry, Organic
Song Liu, Dianmin Zhang, Xiaoqing Zhang, Yuyan Cheng, Hong Deng
Summary: The Ni-catalyzed alkene intermolecular 1,2-dicarbofunctionalization cross-coupling is an efficient method for constructing complex molecules. The computational evidence presented in this report supports a migratory insertion activation mode of alkenes in this reaction. The ligand effect was investigated using bipyridyl as a ligand in the cross-coupling reaction.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Sii Hong Lau, Meredith A. Borden, Talia J. Steiman, Lucy S. Wang, Marvin Parasram, Abigail G. Doyle
Summary: This study introduces a Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides, yielding enantioenriched 2,2-diarylalcohols. Analysis shows that enantioselectivity is correlated with the electronic properties of the ligands, with more electron-donating ligands leading to higher ee values. Experimental and computational studies support the hypothesis that reductive elimination is enantiodetermining and ligand electronic properties affect enantioselectivity by altering the position of the transition state structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Subhadip Roy, Susital Mal, Rupak Banik, Subrata Das, Lubor Dlhan, Jan Titis, Roman Boca, Alexander M. Kirillov, Alexander S. Novikov, Paul Hazendonk, Ray J. Butcher, Antonio Bauza, Antonio Frontera
Summary: This article investigates the synthesis and properties of two new metal(II) complexes [M(dmv)(2)(py)(2)]3H(2)O {M = Ni (1), Zn (2)}. The crystal structures were determined by single crystal X-ray diffraction, and the molecular interactions and magnetic properties were analyzed.
Article
Chemistry, Applied
Mona A. Alamri, Mutlaq. Al-Jahdali, Najlaa S. Al-Radadi, Mostafa A. Hussien
Summary: This study synthesized a series of metal complexes of triazene ligands and characterized them using various analytical methods. The cytotoxic and DNA binding activities of the complexes were studied, revealing that the Zn(II) complex exhibited the highest activity. Molecular docking results correlated well with the cytotoxicity experiments.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Hassan Keypour, Azar Tafazzoli, Seyed Hamed Moazzami Farida, Molood Abdollahi-Moghadam, Robert William Gable
Summary: A new hexaaza Schiff base ligand with a piperazine ring was synthesized and characterized. A novel complex of the ligand with nickel was prepared and characterized, showing a distorted octahedral environment around the nickel ion. The anti-cancer activity and antioxidant property of the ligand and complex were evaluated, and the binding mode of the ligand to nickel ion was investigated using DFT calculations. Theoretical and experimental findings were in agreement.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Physical
V. V. Romaka, L. Romaka, A. Horyn, Yu Stadnyk
Summary: The interaction of Yttrium and Thulium with Nickel and Antimony was studied at 870 K in the whole concentration range, resulting in the formation of several ternary compounds. The electrical resistivity and Seebeck coefficient of the YNiSb and TmNiSb half-Heusler compounds were measured and calculated, showing their behavior as doped and compensated semiconductors.
JOURNAL OF ALLOYS AND COMPOUNDS
(2021)
Article
Chemistry, Organic
Dawei Gong, Degong Kong, Yufei Li, Caiyu Gao, Lina Zhao
Summary: A nickel-catalyzed semihydrogenation of azoarenes to hydrazoarenes with NH3BH3 is developed, exhibiting good functional group tolerance and a high turnover frequency at room temperature. Control and deuterium-labeling experiments reveal that the ethanol hydroxyl and BH3 groups each donated one hydrogen, resulting in the formation of B-(OEt)(3) and H-2 as main byproducts. Density functional theory calculations suggest a ligand-to-ligand hydrogen transfer mechanism for the reaction. This study presents a novel nickel catalytic system for the semihydrogenation of azoarenes.
Article
Chemistry, Physical
Eduardo Jaimes-Romano, Hugo Valdes, Simon Hernandez-Ortega, Rosa Mollfulleda, Marcel Swart, David Morales-Morales
Summary: The catalytic activities of three Ni(II) complexes with fluorinated and non-fluorinated N-heterocyclic carbene (NHC) ligands were evaluated in the C-S cross-coupling reaction. The complexes with fluorinated-NHC ligands exhibited lower catalytic activities compared to the non-fluorinated derivative, attributed to the lower electron-donating character of the fluorinated ligands. Different substrates were tested using complex 3-Ni, achieving varying conversions due to differences in the stability of the intermediates formed.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Sohajl Movahhed, Julia Westphal, Alexander Kempa, Christian Eric Schumacher, Julia Sperlich, Jorg-Martin Neudoerfl, Nicole Teusch, Matthias Hochguertel, Hans-Guenther Schmalz
Summary: Metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, are important target molecules for chemical synthesis due to their pronounced bioactivity. A short and efficient route towards these marine diterpenes has been developed, with notable C-C bond forming transformations. The anti-tubercular agent (+)-erogorgiaene and the pseudopterosin A aglycone were successfully synthesized, exhibiting promising biological activities.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Kaijun Liang, Xuezhi Zeng, Rui Ma, Guojun Zou, Li Dang, Sha Li
Summary: The alloy effect with post-transition metals (Sn, Ga and Bi) on Pt and Ni catalysts during the propane dehydrogenation (PDH) reaction was studied using density functional theory calculations and descriptor-based microkinetic analysis. It was found that alloying with Sn and Bi can enhance propylene selectivity while decreasing activity. Among all catalysts, Bi alloys exhibited the highest propylene selectivity. Ni3Ga outperformed Ni in terms of both PDH activity and propylene selectivity. The formation energies of C3H6 and H were identified as two activity descriptors, with the former also serving as the selectivity descriptor. Further investigation on the structure-activity relationship revealed that at least two descriptors, one geometric parameter (the normalized atom radius) and one electronic parameter (such as d-band center, d-band width, electronegativity), were required to describe the PDH reaction on Pt and Ni-based alloys.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Xiao Su, Fanqi Meng, Hongwei Tan, Guangju Chen
Summary: This study investigated the mechanism of CO2 reduction on a BaTiO3 supported Ni catalyst using density functional theory (DFT). The presence of BaTiO3 was found to play a significant role in the adsorption and activation of CO2. The dominant reaction pathway involves the reduction of CO2 to CH4, with the reduction of CO being the rate-limiting step. The BaTiO3 base induces wrinkling distortion of the Ni surface, facilitating CO hydrogenation, and enhances the binding strength of the catalyst with reaction intermediates.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Multidisciplinary
Nilay Kumar Pal, Kuldeep Singh, Moumita Patra, Suman Yadav, Prabhakar K. Pandey, Jitendra K. Bera
Summary: Oxidative deamination of benzyl amines is achieved using a Ni(ii)-NHC catalyst with water in aqueous medium, resulting in the formation of aldehydes. Water acts as a formal oxidant in this process. The presence of hemilabile pyridyl units in the catalyst facilitates the approach of amines to the metal, allowing nucleophilic water attack on the metal-bound imine. This water-soluble 3d-metal Ni(ii) catalyst with promoter ligands provides a new avenue for water-mediated oxidation reactions.
Review
Multidisciplinary Sciences
Ginny Karir, Eluvathingal D. Jemmis
JOURNAL OF THE INDIAN INSTITUTE OF SCIENCE
(2020)
Article
Chemistry, Inorganic & Nuclear
Selvakumar Balasubramaniam, Sandeep Kumar, Alex P. Andrews, Eluvathingal D. Jemmis, Ajay Venugopal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Sagar Ghorai, Eluvathingal D. Jemmis
Article
Chemistry, Multidisciplinary
Ramkumar Kannan, Selvakumar Balasubramaniam, Sandeep Kumar, Raju Chambenahalli, Eluvathingal D. Jemmis, Ajay Venugopal
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Physical
Sagar Ghorai, Raghavendra Meena, Anju P. Joseph, Eluvathingal D. Jemmis
Summary: The theoretical analysis indicates that the difference in donor-acceptor capabilities of isocyanide and CO ligands controls the product distributions in the reductive coupling reactions mediated by Cr-Cr quintuple bonded complex and B-B multiple bonded complexes. The reactions follow different potential energy surfaces based on the pi-back bonding possibility of CO and isocyanide, leading to products with different spin multiplicities. The reactions also involve changing the oxidation state of boron centers from +I to +II, in contrast to classical main group mediated reactions where stable oxidation states are preserved. This donor-acceptor bonding interaction dominated main group chemistry is more likely to exhibit transition metal behavior.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Review
Chemistry, Multidisciplinary
Eluvathingal D. Jemmis, Sagar Ghorai
Summary: The research focuses on the relationship between boranes and allotropes of elemental boron, addressing various chemical problems such as 1,2-shift in vinyl cations, stability of polyhedral boranes, design of stuffed boron fullerenes, and C-C bond making and breaking processes. The common thread is the use of frontier molecular orbitals for designing, controlling, and explaining chemical observations, introducing Orbital Engineering as a key element in these projects.
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
D. Sravanakumar Perumalla, Sagar Ghorai, Tanmoy Pal, Drahomir Hnyk, Josef Holub, Eluvathingal D. Jemmis
Summary: Closo-carborane anions are more commonly found in literature than the cations. The ionic liquids formed by these two ions, which have similar size and weak coordination, could have significant applications in various areas of chemistry. By studying the rearrangement of dicarboranyl methyl cation, this work sheds light on the synthesis and general interest in carborane cations.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Deepti Sharma, Annabel Benny, Radhika Gupta, Eluvathingal D. Jemmis, Ajay Venugopal
Summary: Primary and secondary interactions play a crucial role in substrate activation, with most activations occurring at the secondary binding site. By exploring ligands with varying nucleophilicity, we found that decreased nucleophilicity can reverse the primary bond to a secondary interaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Rinkumoni Chaliha, D. Sravanakumar Perumalla, Eluvathingal D. Jemmis
Summary: A generalized electron counting rule for borophene with varying hole density explains the preference for hydrogenation in beta(12) borophene. The strength of interaction between the 2D layer and the metal surface is controlled by the interplay between bridging and terminal BH bonds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sagar Ghorai, Eluvathingal D. Jemmis
Summary: The study predicts M2B10H10 and M-2@B10H8 complexes using the inherent coupling tendency of BR fragments, and finds that the metal d-orbitals stabilize the boron wheel structure and form a geometric pattern with Mobius aromaticity in Mn2B10H10. Fe-2@B10H10 has a twisted [10] boraannulene structure. The removal of 2H leads to the planar structures Mn-2@B10H8 and Fe-2@B10H8, stabilized by multicentered (sigma + pi) bonding.
Article
Chemistry, Multidisciplinary
Deepti Sharma, Selvakumar Balasubramaniam, Sandeep Kumar, Eluvathingal D. Jemmis, Ajay Venugopal
Summary: Investigations on the boundaries between the neutral and cationic models of (Mesityl)(2)EX (E = Sb, Bi and X = Cl-, OTf-) have demonstrated a reversal of Lewis acidity from bismuth to antimony. The higher efficiency of (Mesityl)(2)SbOTf over (Mesityl)(2)BiOTf in catalytic reduction of phosphine oxides to phosphines is supported by experiments and computations, providing insights for designing new Lewis acids relevant to catalysis.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Sagar Ghorai, Eluvathingal D. Jemmis
DALTON TRANSACTIONS
(2020)
Article
Chemistry, Multidisciplinary
Jyothish Joy, Eluvathingal D. Jemmis
JOURNAL OF CHEMICAL SCIENCES
(2019)
Article
Chemistry, Multidisciplinary
Ramkumar Kannan, Raju Chambenahalli, Sandeep Kumar, Athul Krishna, Alex P. Andrews, Eluvathingal D. Jemmis, Ajay Venugopal
CHEMICAL COMMUNICATIONS
(2019)
Article
Chemistry, Physical
Jan Machacek, Antonio Frances-Monerris, Naiwrit Karmodak, Daniel Roca-Sanjuan, Jindrich Fanfrlik, Michael G. S. Londesborough, Drahommir Hnyk, Eluvathingal D. Jemmis
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2019)