Article
Chemistry, Physical
Yungen Liu, Ka-Pan Shing, Vanessa Kar-Yan Lo, Chi-Ming Che
Summary: Transition-metal-catalyzed direct C-N bond formation reactions have been widely used for the synthesis of nitrogen-containing compounds. Iron catalysts are promising due to their cost-effectiveness and environmental sustainability, while ruthenium complexes provide more stability for studying the reaction mechanism. This Perspective summarizes the recent developments in iron and ruthenium complexes supported by macrocyclic or polydentate ligands for catalytic amination reactions involving metal imido/nitrene intermediates, and discusses the current limitations and potential opportunities for future research.
Article
Chemistry, Physical
Monica Rodriguez, Aleksandr Y. Pereverzev, Jana Roithova
Summary: A novel octahedral non-heme iron-acyl-nitrenoid complex was presented, and its reactivity was studied using a flow chemistry setup with online mass spectrometry detection. It was found that the iron-acyl-nitrenoid complex can activate C-H bonds via hydrogen-atom transfer and form new N-S bonds in the reaction with thiophenol. However, the reaction with hydrocarbons results in the activation of C-H bonds without a subsequent rebound process.
Article
Chemistry, Multidisciplinary
Dan-Yan Hong, Yungen Liu, Liangliang Wu, Vanessa Kar-Yan Lo, Patrick H. Toy, Siu-Man Law, Jie-Sheng Huang, Chi-Ming Che
Summary: This study reports on Ru(NCOR) intermediates in C-N bond formation catalyzed by [Ru-IV(Por)Cl-2]/N3COR, which is applicable to various chemical reactions with high yields. Experimental studies and DFT calculations support the formulation of Ru(NCOR) acylnitrenoids as a Ru-V-imido species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Rajendra S. Ghadwal
Summary: This paper discusses the tuning of structure and properties of main-group species (E) by controlling pi-conjugation and/or pi-donation using classical N-heterocyclic vinyl (NI-IV) ligands. By selecting appropriate carbene units, the electronic structure of derived species can be precisely controlled, resulting in stable solid materials.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Ali A. Pinarci, Noah Daniecki, Tyler M. TenHoeve, Brandon Dellosso, Rufai Madiu, Liliana Mejia, Seda E. Bektas, Gustavo Moura-Letts
Summary: In this study, the zirconooxaziridine promoted aziridination of alkenes using chloramine T as the quantitative source of N was reported, showing high yields, diastereoselectivities, and stereospecificity for a wide variety of substituted alkenes. A potential mechanism involving the formation of a zirconooxaziridine complex as the active catalyst has been proposed, with initial mechanistic data indicating a highly associative mechanism as the predominant pathway for this transformation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Laura Henrich, Peter C. Mueller, Jan Hempelmann, Markus Mann, Jan van Leusen, Simon Steinberg, Richard Dronskowski
Summary: Fe[C5H5N](2)[N(CN)(2)](2) was synthesized from a reaction of NaN(CN)(2) and FeCl(2) in a methanol/pyridine solution. Crystallographic analysis revealed that the compound crystallizes in the monoclinic space group I2/m (no. 12). The presence of dicyanamide and pyridine was confirmed by spectroscopic and elemental analysis. The compound exhibits high-spin Fe-II state and antiferromagnetic exchange interactions at lower temperatures.
Review
Chemistry, Inorganic & Nuclear
Alec Bigness, Shivaiah Vaddypally, Michael J. Zdilla, Jose L. Mendoza-Cortes
Summary: Heterocubane is a molecular species with a cube-shaped core found in nature, playing a crucial role in important biological reactions. Limited reviews have focused on the significance of the cluster outside of biology, or on the impact of the global coordination environment on reactivity and electronic structure. Understanding the synthetic chemistry of heterocubanes in the context of coordination environment and geometry offers insights into their connection to natural systems.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Organic
Sara Bacaicoa, Ellymay Goossens, Henrik Sunden
Summary: This study presents an accessible aerobic N-heterocyclic carbene (NHC)-catalyzed method for efficiently producing tetrasubstituted benzene rings in a single reaction. The method uses atmospheric oxygen (O2) as the terminal oxidant and employs electron transfer mediators to orchestrate an aerobic oxidation reaction.
Article
Chemistry, Inorganic & Nuclear
Hanhua Xu, Ze-Jie Lv, Junnian Wei, Zhenfeng Xi
Summary: A N-aryloxide-amidine ligand (H3L) was synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps, which integrates phenoxide and amidine ligands through methylene linkers. The coordination modes of the resulting complexes depend on the radius of the metal ions. The ligand can form a dimer (LMIV-Cl)2 with group 4 metal chloride (MCl4)-Cl-IV, and the coordination mode of the amidinate moiety can change from bidentate chelating to bimetallic bridging coordination.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Janis Musso, Jordan De Jesus Silva, Mathis J. Benedikter, Jonas Groos, Wolfgang Frey, Christophe Coperet, Michael R. Buchmeiser
Summary: Recent studies have shown that cationic d(0) group 6 olefin metathesis catalysts exhibit higher activity compared to their neutral counterparts, and their catalytic performance is greatly enhanced by immobilization on silica.
Article
Environmental Sciences
Astha Gautam, Amanda Gomez, Emerita Mendoza Rengifo, Graham N. George, Ingrid J. Pickering, Juergen Gailer
Summary: The exposure of humans to low chronic doses of Cd can have adverse health effects, but the biomolecular mechanisms behind this are not fully understood. In this study, an HPLC-FAAS system was used to investigate the chemistry of Cd2+ in the bloodstream. The addition of L-cysteine to the mobile phase affected the retention behavior of Cd2+, and the formation of CdCys(x)Cl(y) complexes on the column was observed. The formation of these toxicologically relevant Cd species in blood plasma may be implicated in the uptake of Cd into target organs and the resulting toxicological effects.
Article
Chemistry, Multidisciplinary
Nhat Tam Vo, Christian Herrero, Regis Guillot, Tanya Inceoglu, Winfried Leibl, Martin Clemancey, Patrick Dubourdeaux, Genevieve Blondin, Ally Aukauloo, Marie Sircoglou
Summary: In the context of bioinspired OAT catalysis, a new tetradentate dipyrrinpyridine ligand was developed and an unexpected active intermediate was identified in the reaction. The experimental and theoretical evidence combined to provide convincing support for the formation of the active intermediate.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Henry H. Wilson, Xiaojuan Yu, Thibault Cheisson, Patrick W. Smith, Pragati Pandey, Patrick J. Carroll, Stefan G. Minasian, Jochen Autschbach, Eric J. Schelter
Summary: We report a rare and highly reactive lanthanide-ligand complex with multiple bonds. These complexes are important for understanding 4f/5d-bonding in comparison to d-block and actinide congeners. In this study, we isolated and characterized a bridging cerium(IV)-nitride complex: [(TriNOx)Ce(Li2 mu-N)Ce(TriNOx)][BArF4], which is the first molecular cerium-nitride. The compound was obtained by deprotonating a monometallic cerium(IV)-ammonia complex: [CeIV(NH3)-(TriNOx)][BArF4]. The Ce=N bond length in [(TriNOx)Ce(Li2 mu-N)Ce(TriNOx)][BArF4] was determined to be 2.117(3) angstrom. Vibrational and X-ray spectroscopic studies confirmed the +4 oxidation state of cerium, and computational analyses revealed the strong involvement of the cerium 4f shell in bonding.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Thomas G. Linford-Wood, Nathan T. Coles, Ruth L. Webster
Summary: This study reports the reduction of carbon-carbon double bonds using a three-coordinate iron(ii) beta-diketiminate pre-catalyst, employing poly(methylhydrosiloxane) as the hydride donor and a bio-alcohol as the proton source. The results show that allyl arene substrates, styrenes, and aliphatic substrates can all undergo reduction at room temperature using n-butanol and ethanol. Additionally, by changing the deuterium source to d-aniline, high regioselectivity for mono-deuteration of the terminal position of the double bond can be achieved.
Article
Biochemistry & Molecular Biology
William K. Chu, Charles K. Rono, Banothile C. E. Makhubela
Summary: This article reports the anticancer potential of a series of complexes with different ligands and metal centers. Some of these complexes showed cytotoxicity against cancer cells, while most of the compounds displayed poor cytotoxicities. Selected complexes exhibited interactions with model biomolecules. The single atom replacement in the ligand had a significant influence on the cytotoxicity and selectivity to cancer cells.
Article
Chemistry, Multidisciplinary
Gursu Culcu, Diana A. Iovan, Jeremy P. Krogman, Matthew J. T. Wilding, Mark W. Bezpalko, Bruce M. Foxman, Christine M. Thomas
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Multidisciplinary
Matthew J. T. Wilding, Diana A. Iovan, Theodore A. Betley
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Multidisciplinary
Matthew J. T. Wilding, Diana A. Iovan, Alexandra T. Wrobel, James T. Lukens, Samantha N. MacMillan, Kyle M. Lancaster, Theodore A. Betley
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Inorganic & Nuclear
Diana A. Iovan, Shang Jia, Christopher J. Chang
INORGANIC CHEMISTRY
(2019)
Article
Multidisciplinary Sciences
Amymarie K. Bartholomew, Justin J. Teesdale, Raul Hernandez Sanchez, Brian J. Malbrecht, Cristin E. Juda, Gabriel Menard, Wei Bu, Diana A. Iovan, Alexandre A. Mikhailine, Shao-Liang Zheng, Ritimukta Sarangi, SuYin Grass Wang, Yu-Sheng Chen, Theodore A. Betley
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2019)
Article
Multidisciplinary Sciences
Kurtis M. Carsch, Ida M. DiMucci, Diana A. Iovan, Alex Li, Shao-Liang Zheng, Charles J. Titus, Sang Jun Lee, Kent D. Irwin, Dennis Nordlund, Kyle M. Lancaster, Theodore A. Betley
Article
Chemistry, Multidisciplinary
Kurtis M. Carsch, James T. Lukens, Ida M. DiMucci, Diana A. Iovan, Shao-Liang Zheng, Kyle M. Lancaster, Theodore A. Betley
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Jun Ohata, Lakshmi Krishnamoorthy, Monica A. Gonzalez, Tong Xiao, Diana A. Iovan, F. Dean Toste, Evan W. Miller, Christopher J. Chang
ACS CENTRAL SCIENCE
(2020)
Article
Multidisciplinary Sciences
Joel D. W. Toh, Steven W. M. Crossley, Kevin J. Bruemmer, Eva J. Ge, Dan He, Diana A. Iovan, Christopher J. Chang
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2020)
Article
Chemistry, Multidisciplinary
Jeffrey S. Derrick, Matthias Loipersberger, Ruchira Chatterjee, Diana A. Iovan, Peter T. Smith, Khetpakorn Chakarawet, Junko Yano, Jeffrey R. Long, Martin Head-Gordon, Christopher J. Chang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Inorganic & Nuclear
John C. Dickenson, MacKenzie E. Haley, Jacob T. Hyde, Zachary M. Reid, Travis J. Tarring, Diana A. Iovan, Daniel P. Harrison
Summary: The research shows a strong correlation between the redox potentials of metal- and ligand-centered events with the Hammett parameters of aryl substituents. The introduction of a phenyl spacer results in a significant decrease in electron density, affecting the redox properties of homoleptic transition-metal complexes.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Adam C. Sedgwick, James T. Brewster, Peter Harvey, Diana A. Iovan, Graham Smith, Xiao-Peng He, He Tian, Jonathan L. Sessler, Tony D. James
CHEMICAL SOCIETY REVIEWS
(2020)
Article
Chemistry, Multidisciplinary
Diana A. Iovan, Matthew J. T. Wilding, Yunjung Baek, Elisabeth T. Hennessy, Theodore A. Betley
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2017)
Article
Chemistry, Inorganic & Nuclear
K. R. Delle Chiaie, A. B. Biernesser, M. A. Ortuno, B. Dereli, D. A. Iovan, M. J. T. Wilding, B. Li, C. J. Cramer, J. A. Byers
DALTON TRANSACTIONS
(2017)
Article
Chemistry, Multidisciplinary
Diana A. Iovan, Alexandra T. Wrobel, Arthur A. McClelland, Austin B. Scharf, Guy A. Edouard, Theodore A. Betley
CHEMICAL COMMUNICATIONS
(2017)