Article
Chemistry, Applied
Wenli Bai, Jian Sun, Dongyang Wang, Sheng-Di Bai, Liang Deng
Summary: This study investigates the catalytic performance of low-coordinate cobalt(0) N-heterocyclic carbene (NHC) complexes in the hydrosilylation reaction of alkynes, revealing the fine selectivity mechanism governed by the steric nature of the NHC ligand.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Franck Ulm, Saurabh Shahane, Lai Truong-Phuoc, Thierry Romero, Vasiliki Papaefthimiou, Matthieu Chesse, Michael J. Chetcuti, Cuong Pham-Huu, Christophe Michon, Vincent Ritleng
Summary: The preparation of cationic nickel complexes with bidentate coordination and their activity in aldehyde reduction are studied. The nanoparticles involving NHC-picolyl-Ni are observed under specific conditions, showing potential applications in catalysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Inga-Alexandra Bischoff, Bernd Morgenstern, Andre Schaefer
Summary: This study reports a new class of half-sandwich complexes consisting of group 14 elements germanium, tin and lead, which can form complexes with both carbenes and transition metal fragments, bridging the gap between classical N-heterocyclic systems and group 14 metallocenes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Xinyu Du, Xinghao Qi, Kai Li, Xiaoyan Li, Hongjian Sun, Olaf Fuhr, Dieter Fenske
Summary: The novel silylene-supported iron hydride 1 was synthesized via C(sp(3))-H bond activation and exhibited excellent catalytic activity for hydrosilylation of aldehydes and ketones. It showed good tolerance and catalytic activity for substrates with different functional groups on the benzene ring, with both ketones and aldehydes being reduced in good to excellent yields under the same catalytic conditions. A possible catalytic mechanism was proposed based on experiments and literature reports.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Matthieu Cavailles, Oleg A. Filippov, Vincent Cesar, Noel Lugan, Dmitry A. Valyaev
Summary: The first manganese complex with a chiral N-heterocyclic carbene (NHC) ligand was synthesized and characterized. The existence of two isomers with distinct nu(CO) band patterns in solution was revealed by IR spectroscopy. DFT calculations explained their different spectroscopic properties as a result of attractive intramolecular interligand interactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Qi Zhang, Deb Kumar Das, Shuang Yang, Yao Fu, Xinqiang Fang
Summary: The mechanism of N-heterocyclic carbene-catalyzed umpolung of beta,gamma-unsaturated alpha-diketone was found to be more complicated than originally proposed, involving nucleophilic O-acylated homoenolate and electrophilic alpha,beta-unsaturated acyl azolium intermediates. Both DFT calculations and experimental studies confirmed the existence of these key intermediates, leading to a revised mechanism for product formation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kieren J. Evans, Paul A. Morton, Christian Luz, Callum Miller, Olivia Raine, Jason M. Lynam, Stephen M. Mansell
Summary: In this study, various indenyl rhodium complexes were synthesized and tested for their catalytic activities, revealing some complexes exhibited higher catalytic activity than others. These complexes were utilized as catalysts for the borylation of benzene, and the effects of different ligands on catalytic activity were investigated through experiments.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Peng-Shuai Xu, Xin-Hang Jin, Chuan Xie, Qi-Chun Yang, Xiang Zhang, Jun-Long Li
Summary: In this study, a cross-coupling reaction of aldehydes with unactivated alkyl halides was developed through N-heterocyclic carbene catalysis, enabling the synthesis of various ketones. This method offers the advantages of mild reaction conditions and readily available starting materials, and has been successfully applied in the functionalization of pharmaceutical derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Peng-Shuai Xu, Xin-Hang Jin, Chuan Xie, Qi-Chun Yang, Xiang Zhang, Jun-Long Li
Summary: Catalytic cross-coupling reaction of aldehydes with unactivated alkyl halides was achieved via N-heterocyclic carbene catalysis. This method enables rapid synthesis of various ketones from readily available starting materials under mild conditions. The organocatalytic system was successfully applied in the late-stage functionalization of pharmaceutical derivatives. Mechanistic investigations suggest a closed-shell nucleophilic substitution mechanism for this reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sonia Infante-Tadeo, Vanessa Rodriguez-Fanjul, Abraha Habtemariam, Ana M. Pizarro
Summary: This study introduces a new family of osmium arene complexes and investigates their mechanism of action inside cells. The complexes are shown to catalyze the conversion of organic substrates, demonstrating potential anti-cancer drug activity.
Review
Biochemistry & Molecular Biology
Oscar A. Lenis Rojas, Sandra Cordeiro, Pedro V. Baptista, Alexandra R. Fernandes
Summary: The ruthenium arene fragment is a valuable source for designing anticancer drugs, and the co-ligand plays a crucial role in obtaining effective anticancer complexes. N-heterocyclic carbenes (NHCs), despite their versatility and ability to stabilize metal ions, have not been extensively explored. However, recent advancements have been made in the development of NHC ruthenium arene complexes as potent anticancer agents.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Sangeeta Kumari, Charu Sharma, Avinash K. Srivastava, Naveen Satrawala, Kamal N. Sharma, Raj K. Joshi
Summary: A Ru(II) complex was synthesized for C-H bond activation alkenylation of arenes using thioether directing groups, achieving high yields under milder conditions compared to previous methods utilizing precious noble metal catalysts. Broad substrate scope was demonstrated with good tolerance towards benzyl thioethers and vinyl, making it the first report of its kind utilizing a Ru-based catalyst for thioether alkenylation.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Sofia Friaes, Sara Realista, Henrique Mourao, Beatriz Royo
Summary: This article covers the recent progress in the use of N-heterocyclic carbenes (NHCs) in manganese and rhenium catalysis, with a focus on hydrosilylation, hydrogenation, borrowing hydrogen processes, as well as the electrochemical and photochemical reduction of CO2.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Dennis A. Buschmann, Lion Schumacher, Reiner Anwander
Summary: New Cp*(3)Ln(3)(mu(2)-CH3)(3)(mu(3)-CH2)(mu(3)-H)(thf)(3) complexes are formed through the elimination of methane and ethylene, and they exhibit nucleophilic carbene reactivity. Various small-group functionalities can be accessed by treating these complexes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Mustapha El Kadiri, Abdelali Chihab, Rachid Taakili, Carine Duhayon, Dmitry A. Valyaev, Yves Canac
Summary: In this study, different Pd(II) complexes were synthesized and their electronic properties were evaluated by IR spectroscopy data. The impact of different substituents on the overall electronic properties of the complexes was investigated. Furthermore, the effect of oxidatively induced reactions on the structure of the complexes was studied.
Review
Chemistry, Inorganic & Nuclear
Ekaterina S. Gulyaeva, Elena S. Osipova, Ruqaya Buhaibeh, Yves Canac, Jean-Baptiste Sortais, Dmitry A. Valyaev
Summary: This paper provides a comprehensive review of the rapidly emerging application of organometallic manganese complexes in catalytic reactions. It focuses on the influence of different donor ligands on catalytic activity and selectivity, the comparison with polydentate systems, and the study of mechanistic aspects.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Inorganic & Nuclear
Saravanakumar Elangovan, Elisabeth Irran, Hendrik F. T. Klare, Martin Oestreich
Summary: The synthesis and characterization of novel cationic cobalt-(III) thiolate complexes and their ability to promote cooperative, heterolytic Sn-H bond activation have been investigated. It was found that the least congested complex efficiently catalyzes the dehydrogenative homocoupling of nBu3SnH at room temperature.
Article
Biochemistry & Molecular Biology
Mirko Ruamps, Stephanie Bastin, Lionel Rechignat, Alix Sournia-Saquet, Laure Vendier, Noel Lugan, Jean-Marie Mouesca, Dmitry A. Valyaev, Vincent Maurel, Vincent Cesar
Summary: The coordination chemistry of the N-heterocyclic carbene ligand IMes((NMe2)2), and its interaction with transition metal centers, was investigated. The redox behavior of the resulting organometallic complexes was studied, revealing the different oxidation states and their effects on the donating properties of the ligand.
Article
Chemistry, Inorganic & Nuclear
Katarzyna Gajda, Adrian Sytniczuk, Laure Vendier, Bartosz Trzaskowski, Noel Lugan, Anna Kajetanowicz, Stephanie Bastin, Karol Grela, Vincent Cesar
Summary: Three Hoveyda-Grubbs complexes supported by N-(9-alkylfluorenyl)imidazol-2-ylidene ligands were synthesized. The C(sp(3))-H activation of the dangling alkyl group was studied for generating cyclometalated (C,C-NHC) ruthenium complexes for Z-selective olefin metathesis. The methyl derivative led to the expected cyclometalated complex, while no C(sp(2))-H activation of the fluorenyl moiety and no evolution/transformation were observed for the ethyl and benzyl derivatives, respectively. The cyclometalated complex exhibited Z/E stereoselectivity up to 94/6, despite its fragility under catalytic conditions. An unprecedented insertion of the alkylidene moiety into the Ru-C-NHC bond leading to ruthenium N-heterocyclic olefin complexes was also observed and supported by calculations of the corresponding reaction pathway.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Matthieu Cavailles, Oleg A. Filippov, Vincent Cesar, Noel Lugan, Dmitry A. Valyaev
Summary: The first manganese complex with a chiral N-heterocyclic carbene (NHC) ligand was synthesized and characterized. The existence of two isomers with distinct nu(CO) band patterns in solution was revealed by IR spectroscopy. DFT calculations explained their different spectroscopic properties as a result of attractive intramolecular interligand interactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Elena S. Osipova, Sergey A. Kovalenko, Ekaterina S. Gulyaeva, Nikolay V. Kireev, Alexander A. Pavlov, Oleg A. Filippov, Anastasia A. Danshina, Dmitry A. Valyaev, Yves Canac, Elena S. Shubina, Natalia V. Belkova
Summary: The acid-base characteristics of metal hydride complexes can be used to predict their activity in catalytic reactions. The polarity of the M-H bond changes during the formation of a non-covalent adduct with an acidic or basic partner, which is responsible for the subsequent hydrogen ion transfer.
Article
Chemistry, Inorganic & Nuclear
Karim Azouzi, Lucie Pedussaut, Romane Pointis, Anna Bonfiglio, Riddhi Kumari Riddhi, Carine Duhayon, Stephanie Bastin, Jean-Baptiste Sortais
Summary: Manganese, an earth-abundant transition metal, shows great potential as a catalyst for reduction-type reactions. In this study, a simple bis-N-heterocyclic ligand without phosphine associated with manganese complex [Mn(bis-NHCMes)(CO)(3)Br] was found to effectively catalyze the hydrogenation of carboxylic esters in the presence of KBHEt(3) as an activator at high temperature and pressure.
Article
Chemistry, Multidisciplinary
Quentin Le De, Amal Bouammali, Christian Bijani, Laure Vendier, Iker del Rosal, Dmitry A. Valyaev, Chiara Dinoi, Antoine Simonneau
Summary: By experiment and density functional theory (DFT), it is confirmed that the reported direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not exist. Instead, phenylithium reacts with one of the CO ligands to form an anionic acylcarbonyl dinitrogen metallate that decomposes to give a phenylate complex. The DFT calculations support the experimental results, and the direct attack of a nucleophile on metal-coordinated dinitrogen remains to be demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Mohammad Ameskal, Rachid Taakili, Ekaterina S. Gulyaeva, Carine Duhayon, Jeremy Willot, Noel Lugan, Christine Lepetit, Dmitry A. Valyaev, Yves Canac
Summary: An efficient synthesis of stable Pd(II) complexes with diverse coordination frameworks is developed. The complex bearing a nonsymmetrical NHC core pincer scaffold shows competitive donor properties. The bonding situation of C- and P-bound phosphonium ylide fragments within the same molecule is studied for the first time.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Duo Wei, Xinzhe Shi, Ruiyang Qu, Kathrin Junge, Henrik Junge, Matthias Beller
Summary: Chemical hydrogen storage and release processes are crucial for the implementation of new energy vectors. The use of heterogeneous catalytic systems for this purpose is practical and can be easily applied on an industrial scale.
ACS ENERGY LETTERS
(2022)
Meeting Abstract
Chemistry, Multidisciplinary
C. Duhayon, R. Buhaibeh, D. Valyaev, J. B. Sortais, Y. Canac
ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES
(2022)
Article
Chemistry, Multidisciplinary
Duo Wei, Rui Sang, Ayeshe Moazezbarabadi, Henrik Junge, Matthias Beller
Summary: Recent developments in CO2 capture and catalytic hydrogenation to C1 products are discussed in this Perspective, with emphasis on their potential to contribute to a more sustainable energy economy. The catalytic carbon capture and usage (CCU) approach not only reduces CO2 emissions but also provides a foundation for the development of chemical hydrogen batteries.
Article
Chemistry, Multidisciplinary
Elena S. Osipova, Ekaterina S. Gulyaeva, Nikolay Kireev, Sergey A. Kovalenko, Christian Bijani, Yves Canac, Dmitry A. Valyaev, Oleg A. Filippov, Natalia Belkova, Elena S. Shubina
Summary: Low-temperature IR and NMR studies combined with DFT calculations revealed the mechanistic complexity of reactions between Mn(i) complex fac-[(dppm)Mn(CO)(3)H] and Lewis acids, involving the formation of mer-[(dppm)Mn(CO)(3)HMIDLINE HORIZONTAL ELLIPSISLA] and unusual dearomatization of the Ph3C+ cation upon hydride transfer.
CHEMICAL COMMUNICATIONS
(2022)