Article
Chemistry, Inorganic & Nuclear
Bholey Singh, Balaram Pani, Deepak Gupta
Summary: These facial-Re(CO)(3)-based acyclic complexes exhibit unique structural features and strong DNA binding ability, confirmed by X-ray diffraction analysis which shows a variety of intermolecular supramolecular interactions.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Applied
Joanna Palion-Gazda, Barbara Machura, Agata Szlapa-Kula, Anna M. M. Maron, Jacek E. Nycz, Przemyslaw Ledwon, Ewa Schab-Balcerzak, Mariola Siwy, Justyna Grzelak, Sebastian Mackowski
Summary: New rhenium(I) tricarbonyl complexes based on the phenanthroline ligand were designed and synthesized to investigate the role of carbazole and pyrrolidine substituents in determining thermal, electrochemical, and optoelectronic properties. The impact of pyrrolidine and carbazole on the ground and excited-state properties of the complexes were investigated, and the results were supported by theoretical calculations. The HOMO and LUMO energy levels were affected by the substituents, and the structural modification also resulted in noticeable changes in the electrochemical and photophysical behavior of the complexes.
Review
Chemistry, Multidisciplinary
Mohammad Bayat, Davood Gheidari, Morteza Mehrdad
Summary: Ketenimines are reactive species that serve as synthetic intermediates, and have garnered significant interest in recent years, leading to extensive research on their preparation methods and applications.
ARABIAN JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Mohammad Bayat, Davood Gheidari, Morteza Mehrdad
Summary: Ketenimines are reactive species that serve as synthetic intermediates. In recent decades, there has been a significant increase in interest in this class of compounds, leading to extensive research on ketenimine derivatives, including their preparation methods and applications.
ARABIAN JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Chao Zhang, Tingwei Wang, Meiqi Xu, Baolong Kuang, Zhiming Xie, Zujia Lu, Zhenxin Yi, Yan Li, Jianguo Zhang
Summary: This study addresses the challenges of improving detonation performance and mechanical sensitivity in energetic materials. By introducing high-energy structures into pyrazole rings, a new ligand and its corresponding complex were synthesized. The synthesized complex exhibited outstanding explosive initiation capabilities, as demonstrated through comprehensive testing.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Biochemistry & Molecular Biology
Elisabetta Gabano, Mauro Ravera
Summary: Microwave-assisted synthesis has been extensively used in organic synthesis but less exploited in the synthesis of metal complexes. However, it has proven to save time, increase yield and purity, and reduce the risk of decomposition. This review summarizes the results from over 150 papers, suggesting that microwave can be a useful synthetic tool for inorganic chemists.
Article
Chemistry, Multidisciplinary
Sebastian Koniarz, Kinga Szydelko, Michal J. Bialek, Karolina Hurej, Piotr J. Chmielewski
Summary: A family of transition metal complexes based on meso-aryl-2-aza-21-carbaporphyrin (N-confused porphyrin, NCP) derivatives were synthesized and characterized. The chirality of these complexes was demonstrated by enantiomeric separation and analysis. Preliminary catalytic study showed the activity of iridium(III) ortho-metallated complexes in the N-heterocyclization of primary amines with diols.
Article
Chemistry, Inorganic & Nuclear
Xiaowei Pan, Changjiang Wu, Huayi Fang, Chunhua Yan
Summary: Research on lanthanide complexes with silyl ligands is gaining attention, but efforts have been unbalanced for different lanthanide elements. In this study, four types of silyl lanthanide ate complexes were synthesized and structurally characterized. The lanthanum-silicon bonds in these complexes show a polarized covalent feature.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Igor B. Sivaev, Marina Yu Stogniy, Vladimir Bregadze
Summary: This review summarizes the synthesis and structure of transition metal complexes with phosphine ligands derived from icosahedral dicarbaboranes C2B10H12, monocarbaboranes [CB9H10](-), [CB11H12](-), and various metallacarboranes. The possibilities of practical application of such complexes are discussed.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Lili Wang, Johannes Karges, Fangmian Wei, Lina Xie, Zhuoli Chen, Gilles Gasser, Liangnian Ji, Hui Chao
Summary: Conventional photodynamic therapy mainly affects primary tumors, while complementary immunotherapy is effective in eliminating small, non-localized tumors. We report the development of a highly potent immunogenic cell death inducing photosensitizer, Ir-pbt-Bpa, for two-photon photodynamic immunotherapy against melanoma. Upon light irradiation, Ir-pbt-Bpa can induce cell death through a combination of ferroptosis and immunogenic cell death, leading to a strong reduction in tumor size.
Article
Chemistry, Physical
Dustin E. Nevonen, Jenna C. Wagner, Christian Bru''ckner, Christopher J. Ziegler, Victor N. Nemykin
Summary: We systematically investigated Ag(II) and Ag(III) complexes of porphyrins and their analogues using UV-vis magnetic circular dichroism (MCD) spectroscopies and theoretical calculations. Ag(II) and Ag(III) octaethyl- and tetraarylporphyrins showed a typical sign sequence in the Q-band region of their MCD spectra, indicating an HOMO > LUMO relationship. However, Ag(II) complexes of β,β’-pyrrole-modified porphyrins and Ag(III) corroles showed reverse features in the MCD spectra, with an HOMO < LUMO relationship. The Ag(III) complex of N-confused porphyrin exhibited an HOMO > LUMO relationship in the neutral state and an HOMO < LUMO relationship in the protonated form.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ernesto Soto, Katherine L. Helmink, Colleen P. Chin, Michael Ferguson, Steven J. Peters, Lisa F. Szczepura
Summary: Three organometallic rhenium-based clusters containing phenylacetylide ligands were synthesized and characterized. Reactivity studies showed that the formation of vinylidene species did not occur as predicted, but instead the elimination of the acetylide moiety was observed. The isolated reaction products were characterized, and the relative reactivities of the electrophilic agents were compared. Computational studies provided useful information about the nature of the [Re6Se8]2+-acetylide bond and aided in understanding the reactivity of this cluster complex.
Article
Chemistry, Inorganic & Nuclear
Ernesto Soto, Katherine L. Helmink, Colleen P. Chin, Michael Ferguson, Steven J. Peters, Lisa F. Szczepura
Summary: Three rhenium-based clusters with phenylacetylide ligands were synthesized and characterized. Reactivity studies showed that the formation of the predicted vinylidene species did not occur, and instead, elimination of the acetylide moiety was observed. Characterization of the reaction products and computational studies provided insights into the reactivity of this cluster complex.
Article
Chemistry, Medicinal
Jing Liang, Dejuan Sun, Yueying Yang, Mingxue Li, Hua Li, Lixia Chen
Summary: This review explores the clinical potential of organometallic compounds as antimicrobial agents, summarizing common scaffolds and discussing therapeutic targets and risks to be aware of in future studies.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Moonica Martinez-Junquera, Elena Lalinde, M. Teresa Moreno
Summary: The synthesis, structures, and isomerization of a series of alkynyl/isocyanide cycloplatinated compounds and their photophysical properties were studied. The sensitivity and selectivity of two pairs of cis/trans isomers towards Hg2+ were investigated. Trans/cis configuration, cyclometalated ligand, and alkynyl ligand influenced the absorption and emission properties of the complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Dimitrije Djukanovic, Maximilian A. Ganiek, Kohei Nishi, Konstantin Karaghiosoff, Kazushi Mashima, Paul Knochel
Summary: A new convenient method for the preparation of dicarbamoylzincs is reported in this study. The target compounds were obtained by reacting ZnCl2 and formamides or TMP2Zn with formamides. This method is compatible with sensitive functional groups such as esters, ketones, or nitro groups. The reaction of these dicarbamoylzincs with various functionalized allylic, benzylic, aryl, alkenyl compounds, acid chlorides, aldehydes, or enones resulted in the synthesis of polyfunctional amides in high yields. The C-13 NMR characterization of these new compounds is presented.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Daiki Kato, Tomoya Murase, Jalindar Talode, Haruki Nagae, Hayato Tsurugi, Masahiko Seki, Kazushi Mashima
Summary: This study demonstrates the selective synthesis of multifunctionalized ketones using copper salts and aryl Grignard reagents. The method shows good tolerance towards various functional groups and can be applied to the synthesis of important synthetic intermediates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Darryl F. Nater, Christoph J. Kaul, Lukas Laetsch, Hayato Tsurugi, Kazushi Mashima, Christophe Coperet
Summary: Tailored molybdenum (VI)-oxo complexes can catalyze olefin metathesis reaction under specific conditions, and the structural, spectroscopic and electronic characteristics of the catalyst precursor have an influence on the initiation and catalytic efficiency of the final product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Koichi Shinohara, Hayato Tsurugi, Kazushi Mashima
Summary: In this study, a novel lanthanum amide complex was reported as an efficient catalyst for the N-methylation of N-alkylaniline derivatives with CO2 in the presence of PhSiH3. Experimental and computational investigations revealed the crucial role of multiple noncovalent interactions in the reaction mechanism.
Article
Chemistry, Organic
Hayato Tsurugi, Minami Matsuno, Tomomi Kawakami, Kazushi Mashima
Summary: N,N'-Bis(trimethylsilyl)-1,4-dihydropyrazines can be used to synthesize alkylpyrazines by combining with aldehydes and tetra(n-butyl)ammonium fluoride. Various sources of alkyl substituents, such as aryl, heteroaryl, and alkyl aldehydes, can be utilized with good yields obtained from reactions with electron-rich aldehydes. DFT calculations clarified the overall reaction sequence, with the key steps being the activation of the N-trimethylsilyl moiety by fluoride and the subsequent C-C bond formation with aldehydes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Haruki Nagae, Shin-ya Akebi, Saki Matsushiro, Kazutaka Sakamoto, Takanori Iwasaki, Kyoko Nozaki, Kazushi Mashima
Summary: Active methylene compounds, such as nitrile compounds and carbonyl compounds, can act as chain transfer agents in the alternating copolymerization of CO2 and cyclohexene oxide to produce end-functionalized polycarbonates with narrow molecular weight distribution and high carbonate linkage. Acidic nitrile compounds can also result in double chain propagation to form telechelic polycarbonate diols.
Article
Chemistry, Multidisciplinary
Kohei Nishi, Hayato Tsurugi, Kazushi Mashima
Summary: Chromium-catalyzed olefination of aryl aldehydes with haloforms using 2,3,5,6-tetramethyl-N,N'-bis(trimethylsilyl)-1,4-dihydropyrazine (1a) as an organic reducing agent leads to trans-selective formation of beta-halostyrene derivatives. This reaction eliminates the need for metal powders such as zinc and manganese as reductants, reducing metal-based reaction waste.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Mariko Inoue, Hayato Tsurugi, Kazushi Mashima
Summary: Transition metal catalyzed direct C-H activation offers a direct and atom-economical method for constructing new C-C bonds. This review focuses on the unique reactivity of early transition metal complexes towards C-H bonds in heteroatom-containing organic compounds, including pyridine derivatives and alkylamines.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Engineering, Chemical
Taito Kato, Haruki Nagae, Koji Yonehara, Tomoyuki Kitano, Hiroki Nagashima, Shinji Tanaka, Tomoharu Oku, Kazushi Mashima
Summary: This paper discusses the development of anchoring homogeneous Zn or Zr complexes for catalytic transesterification reactions, focusing on the generation of monoesters from acrylates and diols. The immobilized catalysts in a flow reaction system are able to continuously produce monoesterified products without compromising catalytic activities under optimized conditions.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Organic
Yohei Ueda, Hayato Tsurugi, Kazushi Mashima
Summary: Cobalt-catalyzed hydroalkynylation of alkynes, alkenes, and imines allows for the synthesis of internal alkynes with various functional groups adjacent to the carbon-carbon triple bond in an atom-economical manner. In addition, cross-coupling reactions using alkynylcobalt species generated in situ from terminal alkynes, haloalkynes, and metal acetylides selectively provide internal aryl and alkylalkynes.
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We successfully achieved nickel(0)-catalyzed asymmetric allylic alkylation (AAA) of beta-dicarbonyl compounds under ambient conditions by activating unstrained C-C bonds of 2-allylated 2-methylcyclohexane-1,3-dione derivatives. The reaction produced quaternary chiral compounds with high yield and enantioselectivity. The mechanism of the AAA reaction with the Ni(0)-(S)-tol-MeO-BIPHEP catalyst system was elucidated through control experiments and DFT calculations.
Article
Chemistry, Physical
Kohei Nishi, Hayato Tsurugi, Kazushi Mashima
Summary: Chromium(III) trichloride combined with aryl/alkyl Grignard reagents showed high catalytic activity for the synthesis of syn-2-aryl/alkyl-1,2-dihydronaphthalen-1-ols through the ring-opening aryl/alkylation of 7-oxabenzonorbornadiene derivatives. The chromium catalyst allowed the use of unstable aryl Grignard reagents with esters and N-protecting groups. In situ formed diarylchromate(I) from tetraarylchromate(III) was identified as the active species in this catalytic reaction based on control experiments.
Article
Chemistry, Multidisciplinary
Haruki Nagae, Saki Matsushiro, Jun Okuda, Kazushi Mashima
Summary: We discovered that a cationic hetero tetranuclear complex with a calcium and three cobalt ions demonstrated high catalytic activity for the alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO2). The tertiary anilinium salt [PhNMe2H][B(C6F5)(4)] was identified as the best additive to generate the cationic species and maintain polymer selectivity and carbonate linkage, even at 1.0 MPa CO2. Density functional theory calculations revealed that the reaction pathway mediated by the cationic complex is more favorable than that mediated by the neutral complex, with an energy difference of 1.0 kcal mol(-1). Additionally, we found that the exchange of flexible ligands between calcium and cobalt ions is crucial for the smooth proceeding of the alternating copolymerization.
Article
Chemistry, Physical
Kohei Nishi, Hayato Tsurugi, Kazushi Mashima
Summary: Chromium(III) trichloride in combination with aryl/alkyl Grignard reagents exhibited high catalytic activity for the ring-opening arylation reaction of 7-oxabenzonorbornadiene derivatives, producing syn-2-aryl/alkyl-1,2-dihydronaphthalen-1-ols in high yields. The superior catalytic activity of the chromium catalyst allowed the use of unstable aryl Grignard reagents. Control experiments suggested that the in situ formed diarylchromate(I) served as the active species in the catalytic reaction.
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We achieved a nickel(0)-catalyzed asymmetric allylic alkylation reaction of beta-dicarbonyl compounds under ambient conditions, resulting in high yields of quaternary chiral compounds with high enantioselectivity.
