Article
Chemistry, Multidisciplinary
Alexander Okorn, Arumugam Jayaraman, Lukas Englert, Merle Arrowsmith, Theresa Swoboda, Jeanette Weigelt, Carina Brunecker, Merlin Hess, Anna Lamprecht, Carsten Lenczyk, Maximilian Rang, Holger Braunschweig
Summary: The absence of a second ortho-substituent on the boron-bound aryl rings causes the decomposition of the diborane(4) precursors during the reaction process. By reducing the precursors, the desired products can be obtained. The low-lying pi* molecular orbitals located on the PAH substituents lead to a relatively small HOMO-LUMO gap. The hydrogenation reactions of the PAH-substituted diborenes proceed via a different pathway compared to the dimesityldiborene.
Article
Chemistry, Multidisciplinary
Yongliang Wei, Tongdao Wang
Summary: A new route for the synthesis of dinuclear bisborylene complexes was described, and a series of novel diruthenium bisborylenes were successfully prepared. The formation of tris(sigma-B-H) borate played a crucial role in the conversion of trihydroborates to bisborylenes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Andreas Stoy, Merle Arrowsmith, Maximilian Eysselein, Theresa Dellermann, Jan Mies, Krzysztof Radacki, Thomas Kupfer, Holger Braunschweig
Summary: Reduction of B2X4(NHC)(2) yields green 1,2-dihalodiborenes B2X2(NHC)(2) with short B=B double bonds and reversible one-electron oxidation to diboron radical cations. UV-vis, computational analysis, and X-ray diffraction confirm the correlations between properties such as HOMO localization, HOMO-LUMO energies, and chemical reactivity.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Sourav Kar, Alaka Nanda Pradhan, Sundargopal Ghosh
Summary: Metal-rich metallaborane clusters with triply and tetra bridging borylenes, and multicentred boride units have attracted renewed interest due to their diverse reactivity and unique structural features. Recent advancements in synthetic strategies utilizing transition metals have enabled the isolation of borylene species and the encapsulation of boride inside different clusters. The bonding ability of borylene and boride with multiple transition metals has led to the formation of a series of metal-rich metallaboranes.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Jun Fan, Ming-Chung Yang, Ming-Der Su, Cheuk-Wai So
Summary: This work presents a simple method of synthesizing a borylborylene without the need for the rearrangement of a diborene. The reaction of an amidinato amidosilylene and PMe3 with an N-phosphinoamidinato diborane resulted in the formation of a stable silylene-borylborylene and a unstable phosphine-borylborylene. Compound 2 exhibited stability due to the stabilization by the silylene donor and boryl substituent, whereas compound 3 was unstable in solution due to the labile PMe3.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Koushik Saha, Sundargopal Ghosh
Summary: In recent years, there has been significant progress in the chemistry of transition metal borane and borate complexes, particularly in their application in hydrofunctionalisation reactions. This article highlights the important role of these complexes in the hydroboration/hydrosilylation/hydroamination of unsaturated organic species and the isolation of various boron-containing transition metal complexes. Both catalysed and uncatalysed hydroboration reactions using these complexes have shown great potential. Understanding the electronic and steric properties of the borane/borate ligands has facilitated the synthesis of transition metal complexes for use in hydroboration reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Robin Guthardt, Johanna Mellin, Clemens Bruhn, Ulrich Siemeling
Summary: In this study, new ferrocene derivatives and complexes were synthesized and structurally characterized by single-crystal X-ray diffraction. Compounds 1 and 2 represent a new class of ferrocene-based bidentate ligands. Electrochemical investigation revealed the presence of three redox-active moieties in these compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Chaopeng Hu, Lulu Guo, Jianying Zhang, Chunming Cui
Summary: The BNB-embedded indenophenanthrenes 3 were synthesized by reducing LBX2 with potassium graphite under ambient conditions. The formation of 3 likely involves an aminoborylene intermediate and DFT calculations revealed a delocalized BNB 3c-2e interaction in the BNBC2 five-membered ring of 3. Treatment of 3a with IPr led to the coordination of IPr to one of two boron atoms, confirmed by X-ray single-crystal analysis.
Article
Chemistry, Physical
Helgi Freyr Jonsson, Daniel Sethio, Julian Wolf, Stefan M. Huber, Anne Fiksdahl, Mate Erdelyi
Summary: Gold catalysis provides innovative organic transformations with high chemoselectivity under mild conditions. A silver-free route utilizing halogen bonding is presented for gold activation, reducing metal waste and enabling large-scale generation of complex molecules. The recyclability of gold is of supreme importance.
Article
Chemistry, Physical
Patricio Serafini, Alexis Villanueva-Antoli, Samrat Das Adhikari, Sofia Masi, Rafael S. Sanchez, Jhonatan Rodriguez-Pereira, Bapi Pradhan, Johan Hofkens, Andres F. Gualdron-Reyes, Ivan Mora-Sero
Summary: In this study, the introduction of guanidinium (GA+) during the synthesis of high-quality Cs(1-x)GA(x)PbI(3) perovskite nanocrystals (PNCs) was explored as a promising approach for the fabrication of efficient bright-red light-emitting diodes (R-LEDs). The substitution of Cs by 10 mol % GA allowed the preparation of mixed-cation PNCs with PLQY up to 100% and long-term stability for 180 days. This substitution compensated intrinsic defect sites and suppressed the non-radiative recombination pathway, leading to R-LEDs with improved performance and stability.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Rui Guo, Chaopeng Hu, Qianli Li, Liu Leo Liu, Chen-Ho Tung, Lingbing Kong
Summary: This study presents a new isolable diiminoborane compound with a BN analogue of butadiyne structure, which can release and reduce N-2. This discovery has significant implications for the future design of functional main group N-2 species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
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, Organic
Raffaella Papagna, Dana Kutzinski, Stefan M. Huber
Summary: In this study, recyclable polymer-bound halogen bonding catalysts were developed, which exhibited comparable catalytic activity to free halogen bond donors. This proof-of-principle research provides a foundation for the further development of sustainable halogen bonding organocatalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Allegra Franchino, Alex Marti, Stefano Nejrotti, Antonio M. Echavarren
Summary: A library of gold(I) chloride complexes with phosphine ligands incorporating (thio)urea and squaramide H-bond donors was prepared to promote chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in various reactions, including cyclization and tandem reactions. Kinetic studies and DFT calculations suggest that the reaction's energy span is influenced by both the chloride abstraction step and subsequent cyclization step facilitated by the bidentate H-bond donor.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Aaron Forde, Dmitri Kilin
Summary: Lead halide perovskite nanocrystals exhibit exceptional defect tolerance attributed to their unique electronic structure. Surface trap states with A-X vacancies contribute to efficient photoluminescence, although they show enhanced nonradiative recombination rates, reducing photoluminescence quantum yield.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Review
Chemistry, Multidisciplinary
Carel Kwamen, Jochen Niemeyer
Summary: Rotaxanes, as a type of mechanically interlocked molecule, show great potential in the field of catalysis due to their unique three-dimensional structures and flexibility. This Minireview focuses on the use of rotaxanes in organocatalysis and transition-metal catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jan-Erik Ostwaldt, Christoph Hirschhaeuser, Stefan K. Maier, Carsten Schmuck, Jochen Niemeyer
Summary: The study presents a novel supramolecular polymer with a reversed viscosity/temperature profile, formed by ditopic monomers that transform from small cyclic structures at low temperatures to supramolecular polymers at elevated temperatures. The effect is shown to depend on solution concentration and solvent polarity, making the system a potential viscosity index improver in working fluids.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Electrochemistry
Violeta Jevtovic, Khalaf M. Alenezi, Hani El Moll, Ashanul Haque, Jamal Humaidi, Salma A. Al-Zahrani, Dragoslav Vidovic
Summary: Efficient hydrogen production from aqueous protons by direct solar energy conversion is crucial for a future hydrogen economy. This study focuses on the catalytical activity of pyridoxal-semi (H-2-PLSC) and pyridoxal-thiosemi (H-2-PLTSC) carbazone molecules and their iron complexes for electrochemical proton reduction. The complexes showed higher catalytic activity than the free ligands, supporting a proposed mechanism involving protonation of the ligand.
INTERNATIONAL JOURNAL OF ELECTROCHEMICAL SCIENCE
(2021)
Article
Biochemistry & Molecular Biology
Mohammad M. Kamal, Zhizhou Liu, Siyuan Zhai, Dragoslav Vidovic
Summary: Recent evidence suggests that tetra-coordinate borohydride species are the true hydride donors and Me2S-BH3 can act as a hydride donor for imine reduction. This boron reagent is effective and chemoselective for a wide variety of imines.
Editorial Material
Chemistry, Organic
Jochen Niemeyer, Ivo Piantanida, Thomas Schrader
Summary: Carsten Schmuck, a professor of Organic Chemistry at the University of Duisburg-Essen, unexpectedly passed away in 2019, leaving a profound impact on his family, friends, colleagues, students and many others. His legacy is honored through scientific contributions, while his personal influence on individuals he interacted with, including the authors of this editorial, is also remembered.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhizhou Liu, Alasdair McKay, Lili Zhao, Craig M. Forsyth, Violeta Jevtovic, Milena Petkovic, Gernot Frenking, Dragoslav Vidovic
Summary: Introducing a small phosphorus-based fragment into molecules via trapping and releasing reactive phosphorus-based molecules is an important process in synthetic chemistry. This study used electron-rich hexaphenylcarbodiphosphorane to stabilize the least thermodynamically favorable isomer of HO2P and transfer it to various substrates. Additionally, several phosphorus-based compounds were isolated and characterized using this synthetic approach.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Analytical
Dong Hao Wang, Dragoslav Vidovic, Alasdair I. McKay, Tamim Darwish, Hui Gyu Park, Secilia Martinez Garza, Samuel W. Shields, Jennifer S. Brodbelt, Zhen Wang, R. J. Scott Lacombe, Vadim V. Shmanai, Ivan L. Lysenko, Andrei V. Bekish, Karsten Schmidt, Christina Redfield, J. Thomas Brenna, Mikhail S. Shchepinov
Summary: This article describes the deuteration of highly unsaturated fatty acid ethyl esters through Ru-based catalysis and characterizes the extent and kinetics of deuteration using NMR and mass spectrometry analysis.
ANALYTICAL CHEMISTRY
(2022)
Article
Polymer Science
Qamar Un Nisa, William Theobald, Kyle S. Hepburn, Ian Riddlestone, Nathaniel M. Bingham, Maciej Kopec, Peter J. Roth
Summary: In this study, polymers with tailored architectures and degradability were prepared using TARO ATRP. By using appropriate solvents and anhydrous polymerization conditions, degradable copolymers with high thioester content were obtained. Water-soluble molecular brushes were also prepared by adjusting the copolymerization kinetics.
Article
Chemistry, Inorganic & Nuclear
Siyuan Zhai, Craig Forsyth, Zhizhou Liu, Dragoslav Vidovic
Summary: Controlled hydroboration has been developed as an alternative method for the synthesis of mono- and acyclic bis-aminoboranes. The presence of a catalytic aluminum complex improves the purity of the products.
Article
Chemistry, Multidisciplinary
Chloe L. Shaves, Nery Villegas-Escobar, Ewan R. Clark, Ian M. Riddlestone
Summary: The use of a sterically demanding pincer ligand leads to the synthesis of an unusual square planar aluminium complex. Due to the constrained geometry imposed by the ligand scaffold, the four-coordinate aluminium center remains Lewis acidic and exhibits different metal-ligand cooperative pathways for activating ketones and CO2. Furthermore, it demonstrates the rare capability of catalytically reducing CO2 to a methanol equivalent at room temperature as a single-component aluminium system.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Siyuan Zhai, Milena Petkovic, Dragoslav Vidovic
Summary: In this work, it is shown that three-coordinate mono-aminoboranes are not efficient hydroboration reagents unless they can form four-coordinate analogues. It is also demonstrated that imine-BH3 adduct(s) and mono-aminoboranes are not key intermediates in the Me2S-BH3 catalyzed hydroboration of imines. Instead, the Clark mechanism is believed to be mainly responsible for the observed hydroboration reactions in both of these reported studies.
Article
Chemistry, Multidisciplinary
Siyuan Zhai, Dragoslav Vidovic, Milena Petkovic
Summary: We investigated the 1,3-hydride shift during the formation of mono-aminoboranes from imine-BH3 adducts. Experimental and theoretical analyses suggest that this molecular rearrangement can occur through either intra-molecular or inter-molecular pathways. Isotope-based experiments and computational simulations support the bimolecular mechanism. Moreover, our results indicate that elevated temperature is necessary for the formation of mono-aminoboranes by supplying sufficient energy to overcome the reaction barrier.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Deepamali Dissanayake, Craig Forsyth, Dragoslav Vidovic
Summary: This research reports the synthesis and characterisation of several chiral aluminium compounds with oxazoline-containing beta-diketiminate type ligands. These chiral Lewis acid complexes, in combination with 1 equiv. of Na(BAr4Cl), were successfully used as catalysts in asymmetric Diels-Alder reactions between 1,3-cyclohexadiene and various chalcones. Increasing the steric demand of the ligands' achiral end resulted in improved enantioinduction for the cyclisation of 1,3-cyclohexadiene and chalcone. Furthermore, modifying the chiral end by introducing a tert-butyl group to the stereogenic center of the oxazoline fragment yielded the highest enantioselectivity value. The substrate scope was expanded to include several different dienophiles, generating enantiomeric excess values ranging from 24-68%.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Salma A. Al-Zahrani, Violeta Jevtovic, Khalaf M. Alenezi, Hani El Moll, Ashanul Haque, Dragoslav Vidovic
Summary: The study demonstrates the impressive HER catalytic activity of Cu(II) complexes based on pyridoxal semicarbazone and thiosemicarbazone. The catalytic activity of these complexes is not only determined by the central metal, but also influenced by the coordinating ligand.
JOURNAL OF THE SERBIAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Maike Thiele, Frescilia Octa-Smolin, Simon Thoelke, Christoph Woelper, Jurgen Linders, Christian Mayer, Gebhard Haberhauer, Jochen Niemeyer
Summary: Self-assembly of 1,1'-binaphthyl-based bisguanidines and bisphosphoric acids forms a double-helical supramolecular structure, with homochiral pairs forming a left-handed double helix and heterochiral pairs forming a non-helical dimer.
CHEMICAL COMMUNICATIONS
(2021)
