Article
Chemistry, Inorganic & Nuclear
Javier A. Cabeza, Israel Fernandez, Pablo Garcia-alvarez, Ruben Garcia-Soriano, Carlos J. Laglera-Gandara, Ruben Toral
Summary: The compounds H(2)pyrmP(t)Bu(2) and (HpyrmP(i)Pr(2))(2)CMe2 were used to synthesize new P-donor-stabilized stannylenes, demonstrating their potential as precursors to transition metal complexes.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Shuyun Xu, Xuemeng Chen, Gen Luo, Wei Gao
Summary: In this study, two new oxygen-bridged dinuclear Ni(ii) complexes were successfully synthesized by reaction with oxygen in solvent, along with Ni(0) and Ni(i) complexes supported by two neutral ligands. These complexes showed promising catalytic performance at low temperatures.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Jian Xu, Chenshu Dai, Shenglai Yao, Jun Zhu, Matthias Driess
Summary: The paper reports the synthesis of a monoatomic zero-valent tin complex stabilized by a bis(silylene)xanthene ligand and its bis-tetracarbonyliron complex. Density functional theory calculations confirm the genuine stannylone character of the synthesized compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Zufar N. Gafurov, Artyom O. Kantyukov, Alexey A. Kagilev, Alina A. Kagileva, Il'yas F. Sakhapov, Ilya K. Mikhailov, Dmitry G. Yakhvarov
Summary: Pincer complexes are important in organometallic chemistry, especially as homogeneous catalysts for organic transformations. Non-symmetrical phosphorus-based pincer nickel complexes have shown higher catalytic activity and have gained increasing attention in recent years. This mini-review focuses on the recent advances in the chemistry of these complexes, including ligand design, synthesis, and catalytic applications.
Article
Chemistry, Multidisciplinary
Manuel Schmitt, Maximilian Maylaender, Valentin Radtke, Tim Heizmann, Sabine Richert, Ingo Krossing
Summary: The stable and easily accessible salt [Ni(CO)(4)](+)[F{Al(ORF)(3)}(2)](-) was used as a Ni-I synthon to generate novel half-sandwich complexes [Ni(arene)(CO)(2)](+). The reaction with [Ni(o-dfb)(2)](+) salt, which has a rather endergonic reaction, was successful by removing CO irreversibly. The resulting complex has a unique slipped eta(3), eta(3)-sandwich structure and is the ultimate synthon for Ni-I chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sehye Min, Jonghoon Choi, Changho Yoo, Peter M. Graham, Yunho Lee
Summary: This study demonstrates that a special nickel ion, supported by a rigid ligand, can activate C-H and C-O bonds at ambient conditions, playing a crucial role in synthetic applications.
Article
Chemistry, Inorganic & Nuclear
Brenda A. Murueta-Cruz, Armando Berlanga-Vazquez, Diego Martinez-Otero, Luis Norberto Benitez, Ivan Castillo, Alexander Mondragon-Diaz
Summary: Five neutral nickel(II) bimetallic models of the active site of [NiFe]-hydrogenase supported by tridentate sulfur-rich RNS2 ligands were synthesized and tested as electrocatalysts for proton reduction. The b-type complexes with bulky substituents exhibit better catalytic activity compared to the a-type complexes without bulky substituents. This suggests a relationship between the dimer conformation and its catalytic activity, with the Ni center dot center dot center dot Ni cooperative effect playing a crucial role.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
David Gomez de Segura, Nora Gimenez, David Rincon-Monton, M. Teresa Moreno, Jose G. Pichel, Iciar P. Lopez, Elena Lalinde
Summary: A new family of luminescent heteroleptic pentafluorophenyl-bis(2-phenylbenzothiazolyl) Pt-IV derivatives were designed and their photophysical properties were systematically studied. The cationic complexes 1-3 exhibited remarkable efficacy against lung carcinoma and cervix carcinoma cell lines. The neutral complex 6 showed low cytotoxicity and high photocytotoxicity when irradiated with blue light.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Florian J. Ritz, Lars Valentin, Anja Henss, Christian Wuertele, Olaf Walter, Sergei I. Kozhushkov, Armin de Meijere, Siegfried Schindler
Summary: The study investigated the kinetics of reactions between [Ni(bipy)(COD)] and various bicyclopropylidene compounds using stopped-flow techniques. Results supported an associative mechanism and allowed for a more general reaction pathway to be postulated. The structurally characterized nickel(0) and copper(I) complexes exhibited reactivity towards dioxygen, and comparisons were made with similar olefinic complexes in the literature.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maria Frutos, Nasrina Parvin, Antoine Baceiredo, David Madec, Nathalie Saffon-Merceron, Vicenc Branchadell, Tsuyoshi Kato
Summary: A donor-stabilized silylene with a Ni-0-based donating ligand has been synthesized, showing a peculiar behavior due to the cooperative reactivity of Si and Ni centers. Calculations indicate that the orientation of the Ni-ligands with respect to the silylene moiety is crucial in determining the role of the Ni-fragment.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Anastasia A. Fesenko, Mikhail S. Grigoriev, Vladimir B. Arion, Anatoly D. Shutalev
Summary: The unprecedented self-assembly of novel 14-membered cyclic bis-thiosemicarbazone or/and 28-membered cyclic tetrakis-thiosemicarbazone upon acid-promoted cyclooligomerization of 4-(4-thiosemicarbazido)butan-2-one hydrazone has been discovered. By studying the influence of various factors, the optimal conditions for the highly selective formation of each macrocycle have been determined, leading to excellent yields. Plausible pathways for macrocyclizations have been discussed. The macrocycle precursor was prepared by the reaction of readily available 4-isothiocyanatobutan-2-one with an excess of hydrazine.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Connor Fleming, Son Vu, David J. R. Brook, Stefano Agrestini, Eric Pellegrin, Jeffrey Daros
Summary: This study investigates the reaction of nickel and zinc triflates with a tridentate leucoverdazyl ligand, resulting in two neutral coordination compounds. Both compounds undergo ligand-based oxidations in acetonitrile, resulting in an intermediate mixed valence species and a cationic compound.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Sarah M. Craig, Kaycie R. Malyk, Elliot S. Silk, Daniel T. Nakamura, William W. Brennessel, C. Rose Kennedy
Summary: In the past decade, N-heterocyclic carbene, bipyridine, and pyridine oxazoline ligands have been increasingly used in nickel catalysis. The combination of a low-oxidation-state 3d metal and an electron-rich ligand allows for challenging bond activations. This study reports the synthesis and characterization of two Ni(0) complexes supported by a novel bidentate C,N ligand, (h)IMesPy, which shows potential for overcoming reactivity challenges.
JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Neil A. Dodd, Yu Cao, John Bacsa, Eric C. Towles, Thomas G. Gray, Joseph P. Sadighi
Summary: An (N-heterocyclic carbene)nickel(I) cation precursor reacts with the corresponding nickel(0) complex to form a dinickel(I,0) monocation. The Ni···Ni distance in this cation is 0.93 angstrom shorter than in the analogous dinickel(0) complex. Density functional theory calculations indicate significant electronic localization despite equivalent Ni centers in the solid-state structure. Reactions with CO and NO form mononuclear carbonyl and nitrosyl complexes, while oxidative addition of an aryl bromide results in C-arylation of the carbene ligands.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Takashi Mino, Toshiki Yamaoka, Kohei Watanabe, Chihiro Masuda, Shohei Kasano, Yasushi Yoshida, Ryo Takita, Yoshio Kasashima, Masami Sakamoto
Summary: P,olefin ligand/palladium catalyst systems can easily afford the corresponding 2-substituted 3-allylindole derivatives in good to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Jordi Vila, Roger Vinardell, Miquel Sola, Anna Pla-Quintana, Anna Roglans
Summary: Cascade cyclization reactions of 1,5-bisallenes provide access to diverse products through catalyst system tuning and reagent control. Reacting 1,5-bisallenes with dimethyl acetylenedicarboxylate results in diastereoselective formation of cis-3,4-arylvinyl pyrrolidines and cyclopentanes. A proposed mechanism involving a [2+2+2] cycloaddition and cycloisomerization has been supported by DFT calculations.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Biochemistry & Molecular Biology
Anna Pla-Quintana, Anna Roglans
Summary: The [2+2+2] cycloaddition reaction is a fascinating process that creates six-membered rings from three unsaturations with complete atom economy. Rhodium, among the multiple transition metals that can catalyze this reaction, offers advantages such as high activity, versatility, and the ability to easily tune reactivity and selectivity by modifying ligands around the metal. This personal account summarizes efforts in developing efficient and sustainable [2+2+2] cycloaddition reactions, focusing on preparing desired products, developing catalyst recovery and reuse conditions, and understanding mechanistic details governing process selectivity.
Article
Chemistry, Organic
Jordi Vila, Miquel Sola, Anna Pla-Quintana, Anna Roglans
Summary: The synthesis of spiro compounds with seven- and six-membered rings was achieved through a cascade process involving a rhodium(I)-catalyzed cycloisomerization and a highly selective Diels-Alder homodimerization. The scope of the reaction was analyzed using synthetic substrates, and control experiments and DFT calculations were used to explain the observed degree of selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Roger Monreal-Corona, Alex Diaz-Jimenez, Anna Roglans, Albert Poater, Anna Pla-Quintana
Summary: Predictive catalysis was used to study the reaction between pyridinium 1,4-zwitterionic thiolates and a copper carbene. Theoretical calculations were performed to assess the suitability of their annulation reaction and predict the performance of different copper salts, diazo species, and pyridinium derivatives. The experimental conditions were optimized based on these calculations, the scope of the reaction was evaluated, and the accuracy of the predictions was assessed. Indolizine scaffolds were synthesized with yields up to 90% in the reactivity of pyridinium 1,4-zwitterionic thiolates with a metal carbene.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Roger Monreal-Corona, Miquel Sola, Anna Pla-Quintana, Albert Poater
Summary: The mechanism for the stereospecific synthesis of cyclobutanes is revealed using density functional theory (DFT) calculations. The rate-determining step involves the release of N2 from the 1,1-diazene intermediate to form an open-shell singlet 1,4-biradical. The formation of the stereo-retentive product is explained by the barrierless collapse of this open-shell singlet 1,4-biradical. The methodology could potentially be used for the synthesis of [2]-ladderanes and bicyclic cyclobutanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jordi Vila, Miquel Sola, Thierry Achard, Stephane Bellemin-Laponnaz, Anna Pla-Quintana, Anna Roglans
Summary: This article describes the [2 + 2 + 2] cycloaddition of 1,5-bisallenes and alkynes under the catalysis of Rh(I) with hemilabile thioether-functionalized N-heterocyclic carbene ligands. This method effectively provides access to different trans-5,6-fused bicyclic systems with two exocyclic double bonds in the cyclohexene ring. The complete mechanism of this transformation as well as the preference for the trans-fusion over the cis-fusion has been rationalized by density functional theory calculations.
Article
Chemistry, Organic
Alex Diaz-Jimeenez, Stuart C. D. Kennington, Anna Roglans, Anna Pla-Quintana
Summary: The chameleon-like reactivity of pyridinium 1,4-zwitterionic thiolates has been utilized to selectively assemble the 1,4-oxathiin core through a [3 + 3] annulation. The iodonium ylide of cyclic 1,3-diketones was found to be the optimal partner for the annulation reaction. Under copper(I) iodide catalysis, the protocol enables the synthesis of various bicyclic 1,4-oxathiin derivatives under mild conditions. Benzoannulated 1,4-oxathiins have also been successfully accessed through iodine-mediated aromatization of the initially obtained bicyclic compounds.
Article
Chemistry, Organic
Roger Monreal-Corona, Emili Besalu, Anna Pla-Quintana, Albert Poater
Summary: Recent interest has grown in the fusion product of quinoxalinone skeletons and 1,2,3-triazole units due to their agonistic and inhibitory properties. The mechanism for the photoredox-catalyzed synthesis of these scaffolds has been unveiled through DFT calculations, revealing the rate-determining step and predictive chemistry for reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Roger Monreal-Corona, Emili Besalu, Anna Pla-Quintana, Albert Poater
Summary: This study provides mechanistic insights into the functionalization of molecules by N2O through DFT calculations. The rate-determining step of transferring nitrogen or oxygen from N2O to synthesize target structures is revealed. Theoretical calculations show a correlation between the product yield and the energy barrier of the rate-determining step, as well as the potential application of predictive chemistry in the preparation of related compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
