Article
Chemistry, Inorganic & Nuclear
Shanti G. Patra, Nirmal K. Das
Summary: Recent studies on the Grubbs catalyst have shed light on the formation of active intermediates, reaction mechanisms, and the role of the catalyst in chemo-, regio-, and stereoselectivity. Different catalyst structures exhibit varying effects on specific substrates, while chirality and substituents also influence the stereochemistry of the products.
Article
Chemistry, Physical
Haoyu Wang, Haitao Yu, Dong Bai, Dan Yao, Yongjun Han, Yichao Shi, Zhiqun Wang
Summary: A ruthenium olefin metathesis catalyst (C1-H) with a novel NHC ligand tethered by an ethoxy-pyridyl arm was synthesized and compared with its methylated derivative (C1-Me). The study showed profound variations in initiation rate, kinetics, metathesis activity, and decomposition behavior between these two catalysts. The remote torsional strain was found to have a considerable influence on the catalytic activity and decomposition behavior of this ligand class.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Raphael J. Zachmann, Alois Fuerstner
Summary: The newly discovered light-driven gem hydrogenation of alkynes provides a safe and versatile approach to synthesizing Grubbs-type ruthenium carbene complexes, using a triple bond as the carbene source without needing sacrificial phosphines.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Xinrui Ou, Giovanni Occhipinti, Eliza-Jayne Y. Boisvert, Vidar R. Jensen, Deryn E. Fogg
Summary: Ruthenium catalysts bearing cyclic (alkyl)(amino)carbene (CAAC) ligands are highly efficient in olefin metathesis due to their resistance to decomposition. However, turnover numbers in the metathesis of terminal olefins are sensitive to catalyst concentration due to the susceptibility of the methylidene species to decomposition. Understanding the partitioning of CAAC complexes between the precatalyst and the active species is critical for catalyst design.
Article
Chemistry, Physical
Charles Killeen, Jie Liu, Harmen S. S. Zijlstra, Florian Maass, James Piers, Reid Adams, Allen Oliver, J. Scott McIndoe
Summary: Ring-closing metathesis (RCM) is a versatile method for forming cyclic structural elements. Real-time analysis using electrospray ionization mass spectrometry (ESI-MS) was applied to study the RCM reaction, revealing the presence of by-products and the decomposition of the catalyst. Isomerization reactions play a significant role in affecting the yield of the desired product, especially in slow RCM reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Applied
Kamal M. Dawood, Kotohiro Nomura
Summary: This review article summarizes the effects of different catalysts on Z-selective olefin metathesis reactions and the essential roles of ligand modifications in achieving stereospecific reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Chemistry, Physical
Boisvert Y. Eliza-Jayne, Harrison C. Max, Deryn E. Fogg
Summary: Ruthenium dithiolene complexes, known as important olefin metathesis catalysts, exhibit resistance to degradation by amine nucleophiles but are highly sensitive to oxygen.
Article
Chemistry, Inorganic & Nuclear
Geetha S. Remya, Cherumuttathu H. Suresh
Summary: Unlike Ru(II) catalysts, Fe(II) catalysts are ineffective for olefin metathesis. A DFT study reveals that the ineffectiveness of Fe(II) catalysts in CC bond metathesis is due to spin crossover transitions. Additionally, the formation of cyclopropane leads to catalyst degradation.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Henrik Gulyas, Shigetaka Hayano, Adam Madarasz, Imre Papai, Mark Szabo, Agota Bucsai, Eddy Martin, Jordi Benet-Buchholz
Summary: By tuning the electron donor capacity of ligands, air-stable solid adducts of tungsten and molybdenum alkylidenes can be prepared, which can spontaneously release active catalysts in solution.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Thomas G. Pattison, Shuo Wang, Robert D. Miller, Gang-yu Liu, Greg G. Qiao
Summary: Macroscale additive manufacturing has developed significantly, but nanoscale formation of polymeric features from the bottom-up is not yet achieved. This study demonstrates a rapid crosslinking technique using an atomic force microscope, enabling fast curing of crosslinkable polymers in the presence of catalysts.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Christian O. Blanco, Deryn E. Fogg
Summary: Water has a significant impact on olefin metathesis, as it can react with catalysts and cause decomposition of the reaction intermediates. This poses a challenge for demanding reactions in water-rich environments, as metathesis is typically noncatalytic under these conditions.
Article
Chemistry, Physical
Maryana Nadirova, Joel Cejas-Sanchez, Rosa Maria Sebastian, Marcin Wiszniewski, Michal J. Chmielewski, Anna Kajetanowicz, Karol Grela
Summary: Two new unsymmetrical N-heterocyclic carbene ligand (uNHC)-based ruthenium complexes with phenolic OH function were synthesized and characterized. The more active complex was immobilized on the metal-organic framework (MOF) solid support (Al)MIL-101-NH2. The catalytic activity of this heterogeneous system was tested, and although it was less active than the corresponding homogeneous catalyst in solution, it could catalyze selected olefin metathesis reactions, demonstrating the concept of immobilizing catalytically active complexes in MOFs using a phenolic tag.
Article
Chemistry, Inorganic & Nuclear
Seunghwan Byun, Da-Ae Park, Seyong Kim, Sunghyun Kim, Ji Yeon Ryu, Junseong Lee, Sukwon Hong
Summary: A series of acyclic aminooxycarbene (AAOC)-ligated ruthenium metathesis catalysts were developed and exhibited outstanding catalytic efficiencies and selectivities in the ethenolysis of methyl oleate and cis-cyclooctene. The ambiphilic character of AAOC ligands, combining strong sigma-donors and pi-acceptors, contributed to the enhancement of catalytic activity and selectivity of the ruthenium catalysts. This research represents a rare example of acyclic carbene-ruthenium catalysts demonstrating high catalytic efficiency and excellent selectivity in olefin metathesis reactions.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Wietse Smit, Jonas B. Ekeli, Giovanni Occhipinti, Bartosz Wozniak, Karl W. Tornroos, Vidar R. Jensen
Article
Chemistry, Physical
Marco Foscato, Vidar R. Jensen
Article
Chemistry, Physical
Wietse Smit, Marco Foscato, Giovanni Occhipinti, Vidar R. Jensen
Article
Biochemistry & Molecular Biology
Lakshmi Suresh, Ralte Lalrempuia, Jonas B. Ekeli, Francis Gillis-D'Hamers, Karl W. Tornroos, Vidar R. Jensen, Erwan Le Roux
Article
Chemistry, Physical
Daniel L. Nascimento, Immanuel Reim, Marco Foscato, Vidar R. Jensen, Deryn E. Fogg
Article
Chemistry, Multidisciplinary
Daniel L. Nascimento, Marco Foscato, Giovanni Occhipinti, Vidar R. Jensen, Deryn E. Fogg
Summary: The study investigates the bimolecular catalyst decomposition in olefin metathesis, focusing on the susceptibility of emerging ruthenium-cyclic(alkyl)-(amino)carbene (CAAC) catalysts. Through experimental and theoretical analysis, it is found that the faster decomposition of CAAC derivatives is due to stronger trans influence weakening the Ru-py bond. This accelerated decomposition poses a challenge for fast catalyst initiation, highlighting the need to inhibit bimolecular decomposition to enhance catalyst productivity and utility in olefin metathesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Immanuel Reim, Giovanni Occhipinti, Karl W. Tornroos, Deryn E. Fogg, Vidar R. Jensen
Summary: The study focused on the challenging selective transformation of 1-alkenes into E-olefins, designing a series of catalysts with high E-selectivity. By synthesizing Ru21a-c catalysts with specific ligand orientations and analyzing the reaction mechanism through DFT, guidelines were established for pursuing E-selective 1-alkene metathesis.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Gabriel Jeantelot, Simen P. Folkner, Johanna I. S. Manegold, Morten G. Ingebrigtsen, Vidar R. Jensen, Erwan Le Roux
Summary: A catalyst of niobia-supported iridium nanoparticles (Ir@Nb2O5) is reported, which can achieve full conversion of lignin-derived phenols to aromatics under mild conditions with appreciable selectivity.
Article
Chemistry, Physical
Jonas Himmelstrup, Vidar R. Jensen
Summary: Samarium diiodide (SmI2) is an important reductant used in various applications. However, the prediction of its redox and proton-coupled electron transfer reactions using conventional density functional approximations is highly inaccurate. The discrepancy is mainly due to the delocalization error, which leads to destabilization of Sm(III) compared to Sm(II). Including spin-orbit coupling and virtual orbitals in the calculations can help reduce the error. Parametrized double-hybrid methods show promise in further developing the chemistry of SmI2.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Xinrui Ou, Giovanni Occhipinti, Eliza-Jayne Y. Boisvert, Vidar R. Jensen, Deryn E. Fogg
Summary: Ruthenium catalysts bearing cyclic (alkyl)(amino)carbene (CAAC) ligands are highly efficient in olefin metathesis due to their resistance to decomposition. However, turnover numbers in the metathesis of terminal olefins are sensitive to catalyst concentration due to the susceptibility of the methylidene species to decomposition. Understanding the partitioning of CAAC complexes between the precatalyst and the active species is critical for catalyst design.
Article
Chemistry, Multidisciplinary
Giovanni Occhipinti, Daniel L. Nascimento, Marco Foscato, Deryn E. Fogg, Vidar R. Jensen
Summary: This study investigates the factors promoting or inhibiting β-H elimination in the metathesis of alcohols and styrene using silicon-cyclic (alkyl)(amino)carbene (CAAC) catalysts and N-heterocyclic carbene (NHC) catalysts. The results show that CAAC catalysts have a stronger trans effect, which inhibits β-H elimination. However, the strong trans effect of CAAC catalysts also accelerates other decomposition pathways of the catalyst.