Article
Chemistry, Inorganic & Nuclear
Liam K. Burt, Anthony F. Hill
Summary: The nature of the W=C-Pt carbido bridge was investigated through the synthesis of a series of complexes. The results showed that disubstitution occurs for aryl isocyanides, while monosubstitution occurs for alkyl isocyanides.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mahmoud T. Abo-Elfadl, Ahmed M. Mansour
Summary: Complex 4 decorated with benzimidazole moiety was found to be harmless to normal mice splenocytes. Fluorescence microscopy revealed that complex 2 exhibited the highest levels of apoptotic and necrotic alterations in the MCF-7 cell line.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Lachlan J. Watson, Anthony F. Hill
Summary: The pro-ligands react with [RhCl(CE)(PPh3)2] to form bimetallic complexes, which undergo double C-H activation to form N-heterocyclic carbene (NHC) pincer complexes. Reduction and treatment with tritylium, ferrocenium or triphenylcyclopropenium tetrafluoroborates result in the formation of mononuclear NHC pincer complex salts. Treatment with lithium (trimethylsilyl)acetylide provides another bimetallic species, which can be obtained from [RhCl(RPm)] and LiCuCSiMe3.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Federica Battistin, Thomas Fox, Olivier Blacque, Roger Alberto
Summary: The synthesis of sandwich complexes of rhenium is limited to [Re(eta 6-arene)2]+ compounds via the Fischer-Hafner approach, which is not compatible with functionalized arenes. However, functionalized arenes can exchange naphthalene in [Re(eta 6-C6H6)(eta 6-C10H8)]+ and [Re(eta 6-C10H8)2]+ with low to medium yields. In contrast, cyclic nonaromatic polyenes can exchange naphthalene with good to very good yields. This study reports the synthesis of highly stable rhenium sandwich complexes with seven-and eight-membered rings bearing multiple double bonds, starting from [Re(eta 6-C6H6)(eta 6-C10H8)]+ and [Re(eta 6-C10H8)2]+.
Article
Chemistry, Multidisciplinary
Richard A. Manzano, Anthony F. Hill
Summary: This passage mainly introduces the synthetic method and reactions of the new fluorocarbynes [M(CF)(CO)(2)(Tp*)]. The [M(CF)(CO)(2)(Tp*)] are obtained by electrophilic fluorination of the lithiocarbynes [M(CLi)(CO)(2)(Tp*)], and react with [AuCl(SMe2)] and PhICl2 to yield the first m2-fluorocarbyne complex [WAu(m-CF) Cl(CO)(2)(Tp*)] and the first high oxidation state fluorocarbyne [W(<^>CF)Cl-2(Tp*)], respectively.
Article
Chemistry, Inorganic & Nuclear
Kokila Ranasinghe, Patricia A. Marzilli, Svetlana Pakhomova, Luigi G. Marzilli
Summary: This study investigates the stability and ligand dissociation properties of a series of coordination compounds by synthesizing different ligands. Some ligands exhibit high stability in solution, while others undergo ligand dissociation.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Platon Chernavin, Kseniya Maryunina, Gleb Letyagin, Galina Romanenko, Sergey Tumanov, Sergey Veber, Matvey Fedin, Artem Bogomyakov, Victor Ovcharenko
Summary: A one-step synthesis method of paramagnetic Re(I) compounds was developed by reacting [Re(CO)(5)Br] with spin-labeled N-donor heterocycles. Nitronyl nitroxide derivatives of 1H-imidazole (L-1), 1H-pyrazole (L-2), di (1H-pyrazol-1-yl)methane (L-3), and 4-methyl-2-(1H-pyrazol-1-yl)quinoline (L-4) could replace two CO molecules in [Re(CO)(5)Br], leading to the formation of paramagnetic fac-[Re(CO)(3)(L-i)(n)Br]center dot xSolv complexes. The coordination of paramagnetic L-1-L-4 ligands to Re(I) was confirmed by single crystal XRD studies. Magnetic behavior analysis showed that complexes 1-3 were biradicals, while complex 4 was a monoradical. The therapeutic properties of Re(I) and the contrasting characteristics of nitroxide radicals make [Re(CO)(3)(L-i)(n)Br] valuable model objects for material design in theranostics.
Article
Chemistry, Inorganic & Nuclear
Diana Aleksanyan, Svetlana G. Churusova, Ekaterina Yu Rybalkina, Zinaida S. Klemenkova, Gleb L. Denisov, Vladimir A. Kozlov
Summary: New ditopic pincer ligands with an oxalamide core and phosphorus(V) pendant arms were successfully synthesized by reacting ortho-(thio)phosphorylated anilines with oxalyl chloride. The thiophosphoryl-functionalized ligand could undergo direct cyclometalation to form the desired Re(I) pincer complex, while the phosphoryl-containing ligand led to a complex mixture of products.
Article
Chemistry, Inorganic & Nuclear
Kelly L. Rue, Jeffrey R. McLachlan, Juliana A. Cazzaniga, Indranil Chakraborty, Christopher J. Dares, Raphael G. Raptis
Summary: Four new structurally similar dinuclear oxorhenium(V) complexes have been synthesized and characterized, showing little variation in spectroscopic features. All complexes exhibit a bent Re-O-Re core and distorted octahedral coordination geometry. A reversible one-electron electrochemical process is observed at approximately 0.84 V vs. Fc(+)/Fc in all four complexes, with a slight destabilization of the oxidized Re(VI) center when changing the terminal halide from chloride to bromide.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Liam J. J. Stephens, Elena Dallerba, Jenisi T. A. Kelderman, Aviva Levina, Melissa V. V. Werrett, Peter A. A. Lay, Massimiliano Massi, Philip C. C. Andrews
Summary: This study synthesized and characterized twelve Re(i) tricarbonyl diimine complexes with thiotetrazolato ligands. The tetrazolato ligand can bind to the Re(i) center through either the S atom or the N atom, with most complexes being bound to the N atom. In solution, the complexes exist as an equilibrating mixture of linkage isomers. The complexes exhibit photoluminescent properties, with emission wavelengths dependent on the nature of the diimine ligand.
DALTON TRANSACTIONS
(2023)
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)
Review
Chemistry, Multidisciplinary
Bhavin Siritanaratkul, Catherine Eagle, Alexander J. Cowan
Summary: The electrochemical reduction of CO2 provides a sustainable approach for generating carbon-based fuels and feedstocks. Manganese carbonyl complexes, with their ease of synthesis and use of abundant transition metal, are interesting catalysts for this process. The selectivity of these catalysts in the presence of weak Bronsted acids is due to a proton-assisted CO2 binding mechanism. Our research demonstrates the use of manganese carbonyl complexes in water and validates the proposed mechanism through spectroelectrochemistry.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Mengfei Wang, Kei Murata, Yosuke Koike, Gediminas Jonusauskas, Amaury Furet, Dario M. Bassani, Daisuke Saito, Masako Kato, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Kazuyuki Ishii
Summary: A recent study has demonstrated the photo-induced CO-releasing capabilities of the complex Re1Pc, which is composed of a [Re(CO)(3)](+) unit and a phthalocyanine ligand. The complex exhibited efficient spin-orbit coupling and large Franck-Condon factors, resulting in short excited-state lifetimes and ultrafast intersystem crossing. This research provides promising insights into the development of red-light-driven photoCORMs for biomedical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Suman Sinha, E. Muhammed Sahad, Rakesh Mondal, Siuli Das, Litty Thomas Manamel, Paula Brandao, Bas de Bruin, Bikas C. Das, Nanda D. Paul
Summary: In this study, a ligand-centered redox-controlled strategy was used to synthesize an unusual binuclear diradical cobalt(III) complex. The complex showed promising potential for application as a molecular memory device.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Fanqiang Meng, Shogo Kuriyama, Hiromasa Tanaka, Akihito Egi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: A series of rhenium complexes with pyridine-based PNP-type pincer ligands are synthesized from rhenium phosphine complexes. These complexes catalyze the conversion of dinitrogen into ammonia and silylation of dinitrogen under mild reaction conditions, demonstrating the successful catalytic nitrogen fixation using rhenium-dinitrogen complexes as catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Annie L. Colebatch, Benjamin J. Frogley, Anthony F. Hill, Chee S. Onn
Summary: The chemistry of transition metal carbynes has traditionally been dominated by species with hydrocarbyl or amino substituents, but there is a recent emergence of carbynes with other main-group substituents, particularly heavier elements of the p-block. This review focuses on the chemistry of heavier pnictogen-functionalised C-1 ligands and discusses recent developments in related phospha-isonitrile and cya-phosphide ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Richa Gupta, Dipendu Mandal, Amit K. Jaiswal, Rowan D. Young
Summary: This study presents a frustrated Lewis pair (FLP)-catalyzed monoselective C-F activation method for a range of aliphatic polyfluorocarbons with equivalent geminal and distal C-F positions, which can be further functionalized through various reactions.
Article
Chemistry, Multidisciplinary
Qingyang Wang, Richard A. Manzano, Hendrik Tinnermann, Simon Sung, Baptiste Leforestier, Tobias Kraemer, Rowan D. Young
Summary: The use of PCcarbeneP pincer ligands allows for metal-ligand cooperative reactivity and support for a variety of iron oxidation states, making it potentially useful in catalytic applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hendrik Tinnermann, Simon Sung, Daniel Csokas, Zhi Hao Toh, Craig Fraser, Rowan D. Young
Summary: In this study, weak adducts between Li+ and Na+ cations and a neutral iron(0) complex were reported, which synergistically activate aliphatic C-X bonds and lead to the formation of iron(II) organyl compounds. The system showed potential for homocoupling and crosscoupling reactions. Further investigation on the activation mechanism revealed a cooperation between the alkali metal and iron(0) center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Inorganic & Nuclear
Richard A. Manzano, Rowan D. Young
Summary: The PCcarbeneP pincer ligands were slow to develop after their discovery in the early 20th century, but have seen renewed activity in the last 10-15 years, with practical solutions allowing for their application on various metals. These ligands exhibit unique reactivity and diversity, showing the ambiphilic nature of the carbene position.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Benjamin J. Frogley, Anthony F. Hill
Summary: The reactivity of tungsten diphenylarsinocarbyne and its formation of complexes with different metal centers, particularly with gold(i), are discussed. The treatment with MeOSO2CF3 results in methylation at arsenic, leading to the formation of arsoniocarbyne. This provides a new example of coordination chemistry involving tungsten and gold.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Clarence Tan, Hendrik Tinnermann, Simon Sung, Li Heng Kat, Rowan D. Young
Summary: This report discusses the synthesis and characterization of a series of symmetric and asymmetric PCcarbeneP pincer complexes through a proligand dehydration approach. The study found that introducing sterically encumbering aryl substituents at the pincer phosphino positions can impart selectivity to the complexes.
Review
Chemistry, Organic
Richa Gupta, Rowan D. Young
Summary: Halodefluorination of alkyl fluorides using group 13 metal halides is a well-known reaction that has undergone significant developments in recent years, including the use of various metal halide sources, development of catalytic processes, and selective halodefluorination in polyfluorocarbons.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Shivashankar Khanapur, Kenneth Lye, Dipendu Mandal, Xin Jie Wee, Edward G. Robins, Rowan D. Young
Summary: We present a general method for labeling both CF3 and CF2H groups in various chemical settings. The method provides good radiochemical yields and molar activities, and is applicable to biologically relevant compounds. The use of target compounds as starting materials and the simplicity of the method make it attractive for drug and radiotracer development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Clarence Tan, Hendrik Tinnermann, Vanessa Wee, Shaun Tan, Simon Sung, Qingyang Wang, Rowan D. Young
Summary: The reaction of alkynes with PC carbene P complex 1 leads to the formation of 773-benzo-A.5-phosphinine rhodium complexes 2. By reacting two equivalents of 1 with diynes, bimetallic 773-benzo-A.5-phosphinine rhodium complexes 3 can be easily accessed. Compounds 2a-c,e and 3a-c were synthesized and characterized, and their performance as catalysts in the hydrosilylation of alkynes was tested. Bimetallic complexes 3a-c showed enhanced activity compared to monometallic and monocationic analogues 2d, with improved yields and reaction rates.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Daniel Csokas, Richa Gupta, Pragati K. Prasad, Kelvin K. K. Goh, Rowan D. Young
Summary: Aluminum acts as an independent halodefluorination reagent in the reaction, where a heavier halogen replaces aliphatic fluorine. The role of catalytic aluminum halide and organyl alane reagents is not fully understood. Computational and experimental results suggest that the observed reactivity trends between different halide reagents can be attributed to relative barriers in halide delivery to the organic fragment, which is the rate-limiting step in both aluminum halide- and B(C6F5)3-catalyzed pathways.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Liam K. Burt, Anthony F. Hill
Summary: The nature of the W=C-Pt carbido bridge was investigated through the synthesis of a series of complexes. The results showed that disubstitution occurs for aryl isocyanides, while monosubstitution occurs for alkyl isocyanides.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhi Hao Toh, Hendrik Tinnermann, Dinh Cao Huan Do, Han Vinh Huynh, Tobias Kramer, Rowan D. Young
Summary: We isolated and characterized the gold(i)-iron(0) adducts and found that the gold-iron interaction is predominantly a sigma-donation from iron to gold. The Pr-i(2)-bimy carbenic C-13 NMR signal can be used to gauge the relative donor strength of Fe(0) donors.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Liam K. Burt, Rian D. Dewhurst, Anthony F. Hill, Richard Y. Kong, Emily E. Nahon, Chee S. Onn
Summary: This study reports a series of rare mu(2)-halocarbyne complexes and characterizes and analyzes them through experimental and computational methods.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Ryan M. Kirk, Anthony F. Hill
Summary: This study reports the first examples of late transition metal eta(5)-arsolyls serving as ditopic donors to extraneous metal centres through both conventional and polar-covalent interactions.
