Article
Chemistry, Multidisciplinary
Mirela A. Farcas-Johnson, Sara H. Kyne, Ruth L. Webster
Summary: We describe the iron-catalyzed polymerizations of diol and silane monomers to obtain various poly(silylether) products. The reactions are simple and applicable to different types of silane and diol substrates. The obtained materials exhibit low T-g values and high thermal stability, with the use of 2 degrees silane leading to higher thermal stability compared to 1 degree silane.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Kevin Lindenau, Nora Jannsen, Mirko Rippke, Hanan Al Hamwi, Carmen Selle, Hans-Joachim Drexler, Anke Spannenberg, Mathias Sawall, Klaus Neymeyr, Detlef Heller, Fabian Reiss, Torsten Beweries
Summary: The catalytic dehydrocoupling of H3B·NMe2H using Cp2Zr(Cl)(μ-Me3SiC3SiMe3)Zr(Cl)Cp-2 (1)/MeLi was studied, revealing the formation mechanism of Zr amidoborane and hydride species. Unusual dinuclear complex Cp2Zr(C2SiMe3)(μ-R)ZrCp2 (R = CH(2)SiMe3, 7; R = H, 9) formed through activation of the allenediide unit of the precatalyst 1 was identified as potential single-component catalysts for the dehydrocoupling of amine boranes.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
P. Veeraraghavan Ramachandran, Henry J. Hamann, Randy Lin
Summary: A highly versatile synthesis of amine-boranes has been achieved through carbonyl reduction by sodium borohydride, resulting in the production of borane complexes with various amine functionalities and phosphines. This method allows for the activation of sodium borohydride using aldehydes and ketones as the carbonyl source, leading to the formation of borane reactive functionalities and heteroarylamines.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Callum R. Woof, Thomas G. Linford-Wood, Mary F. Mahon, Ruth L. Webster
Summary: A rare study on the catalytic hydrophosphination of allenes has been reported. Using an Fe(II) ss-diketiminate pre-catalyst, HPPh2 can react with aryl- and alkylallenes, with the major product being the E-vinyl. Good yields of the 1,1-disubstituted alkene can be achieved using H2PPh, and the resulting secondary phosphine product does not undergo further reaction. A catalytic cycle hypothesis has been proposed based on spectroscopic data. On the other hand, using an [Fe(salen)](2)-mu-oxo pre-catalyst leads to phosphine dehydrocoupling instead of hydrophosphination.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Callum R. Woof, Derek J. Durand, Ruth L. Webster
Summary: An iron(II)-catalyzed polymerization of arylallenes has been reported, generating high molecular weight polymers at room temperature. The polymer structures and chain lengths of various monomers were determined using NMR, DSC, and GPC analysis. Mechanistically, it is proposed that chain growth occurs through a reactive Fe(III) species, rather than the formation of an iron(II) hydride in situ.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Kevin Turani-I-Belloto, Rodica Chiriac, Francois Toche, Eddy Petit, Pascal G. Yot, Johan G. Alauzun, Umit B. Demirci
Summary: Three new amine borane adducts (ABAs), C3AB, C2C6AB, and (C12)2AB, were synthesized and characterized. The presence of B-N bonds and dihydrogen bonds (DHBs) were confirmed by various techniques, including FTIR, Raman, and NMR. Thermal analysis and calculations demonstrated that (C12)2AB exhibited higher stability and could be potentially used for the synthesis of advanced materials.
Article
Chemistry, Inorganic & Nuclear
Huajin Feng, Dawei Yang, Tao Mei, Yahui Zhang, Baomin Wang, Jingping Qu
Summary: Multinuclear metal thiolate complexes are important organometallic compounds that can serve as bio-mimicking functional platforms and excellent cooperative catalysts. By synthesizing new sulfur-containing ligands, unstable metal ions can be stabilized to generate new thiolate-bridged bimetallic complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Emaad M. A. Al-Janabi, Mohammad R. Hatshan, Syed Farooq Adil, Wesam R. Kadhum, Subhi A. Al-Jibori, Ahmed S. Faihan, Ahmed S. Al-Janabi
Summary: A series of new platinum(II) mixed ligand complexes have been synthesized and characterized, showing promising biological activity against pathogenic bacteria and lung cancer cells. Some complexes exhibited significant anti-bacterial and anti-cancer properties, highlighting their potential for further investigation.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Inorganic & Nuclear
Georgia M. Richardson, Jesse Howarth, Matthew J. Evans, Alison J. Edwards, Scott A. Cameron, Mathew David Anker
Summary: Cyclopentadienyl ligands are commonly used to stabilize low-valent lanthanide(II) complexes, and in this study, the reactions of beta-diketiminate ytterbium(II) hydride with various compounds were reported. The resulting heteroleptic ytterbium(II) cyclopentadienides were characterized and found to exist as mononuclear species in both solution and solid state, with the ytterbium(II) center retaining its oxidation state.
JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Brant Maitland, Andreas Stasch, Cameron Jones
Summary: This article describes a new type of calcium and ytterbium complexes, which only contain β-diketiminate calcium and ytterbium ligands without donor solvents. The article also reports a C-H activated product of β-diketiminate calcium and a contact ion pair ytterbium compound.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Valentyn Pozhydaiev, Marie Vayer, Claire Fave, Joseph Moran, David Leboeuf
Summary: We report a new one-pot protocol for the synthesis of beta-arylethylamines, which allows the direct entry to unprotected compounds with remarkable functional group tolerance. This method involves the 1,2-aminoarylation of alkenes using hydroxylammonium triflate salts and (hetero)arenes. The combination of hexafluoroisopropanol as a solvent and an iron(II) catalyst is crucial for the synthesis of nitrogen-containing molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Reon Ishii, Minesato Nakagawa, Yoshimasa Wada, Yusuke Sunada
Summary: （English Summary:）
In this study, several iron complexes were successfully synthesized through ligand exchange reactions and the introduction of different coordinating organosilyl ligands. The catalytic performance of these complexes in the hydrosilylation reaction was investigated, and the results showed that the square-planar iron(ii) complex with trans-oriented organosilyl ligands exhibited superior reactivity.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Applied
Xiaoxu Ma, Mong-Feng Chiou, Liang Ge, Xiaoyan Li, Yajun Li, Li Wu, Hongli Bao
Summary: The study presents the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes. The reaction is practical and requires relatively low loading of catalyst, with mechanistic studies confirming the radical nature and unusually low activation energy. This work may contribute to elucidating the mechanism of iron-catalyzed azidation and inspire further studies and applications.
CHINESE JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Bappaditya Goswami, Manas Khatua, Subhas Samanta
Summary: In this study, four Co(II) complexes were synthesized and characterized using various techniques. Their catalytic activity in styrene polymerization was evaluated, with complex 3 showing the highest efficiency among the azo-aromatic complexes, while the imine-based complex 4 exhibited lower activity.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Matthew Allison, Pablo Carames-Mendez, Christopher M. Pask, Roger M. Phillips, Rianne M. Lord, Patrick C. McGowan
Summary: The new bimetallic ruthenium-iron complexes show strong anti-cancer potential in cytotoxicity experiments, especially in targeting hypoxic tumor regions. Additionally, these complexes demonstrate good potential in damaging DNA and inhibiting bacterial and fungal growth.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Thomas G. Linford-Wood, Mary F. Mahon, Matthew N. Grayson, Ruth L. Webster
Summary: This paper presents a synthetic study into the catalytic hydrogen/deuterium exchange of 1 degrees silanes, 2 degrees silanes, and 3 degrees siloxanes facilitated by iron-beta-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for various aryl- and alkyl-containing hydro-silanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin) with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.
Article
Chemistry, Multidisciplinary
Kyle G. Pearce, Chiara Dinoi, Michael S. Hill, Mary F. Mahon, Laurent Maron, Ryan S. Schwamm, Andrew S. S. Wilson
Summary: The synthesis and catalytic properties of hydrocarbon-soluble beta-diketiminato phenylcalcium derivatives are discussed in this article. The compounds display different modes of Ca-mu(2)-Ph-Ca bridging and can selectively and uncatalyzedly form biaryls when reacted with aryl bromides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Emma Richards
Summary: Ionic compounds containing sodium cations are known for their stability and resistance to redox reactivity. However, when treated with non-reducible organic bases, a low oxidation state {Mg2Na2} species undergoes selective extrusion of sodium metal and oxidation of the Mg-I centers. Quantum chemical studies indicate that intramolecular electron transfer is facilitated by the molecular orbitals of the {Mg2Na2} ensemble.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Laura E. English, Thomas M. Horsley Downie, Catherine L. Lyall, Mary F. Mahon, Claire L. McMullin, Samuel E. Neale, Carla M. Saunders, David J. Liptrot
Summary: The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane resulted in the formation of boraformamides, pinBN(R)C(O)H, in most cases. Overreduction was observed only for electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis revealed that the stability of [(IPr)CuH](2), proposed as the catalyst resting state, influences selectivity and offers a potential solution to prevent overreduction in future work. In the case of iPrNCO, the formation of [(IPr)CuH](2) prevents overreduction kinetically. However, for 4-NC-C6H4NCO, the barrier height for the first step of overreduction is much lower, resulting in unselective reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kyle G. G. Pearce, Michael S. S. Hill, Mary F. F. Mahon
Summary: Reaction of BeCl2 with dilithium diamide yields the dimeric chloroberyllate, leading to the formation of a 2-coordinate beryllium amide. Reduction of the beryllium amide using lithium or sodium in benzene produces relevant organoberyllate products, likely through transient Be(i) radicals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jinxiong Lin, Daniel S. Frost, Nathan T. Coles, Manuela Weber, Christian Mueller
Summary: A series of novel 3-N,N-dimethylaminofunctionalized phosphinines were synthesized and characterized. DFT calculations showed their stronger pi-donor and sigma-donor properties compared to C5H5P. Complexes of [(phosphinine)(2)CuBr](2) and mononuclear phosphinine-Au(I)Cl were obtained and characterized. The presence of SiMe3-group and donor-functionality allows for post-synthetic ligand modifications. A rare Cu(I) complex with a Cu4Cl4-core, containing two pairs of differently coordinating phosphinine ligands, was formed with CuCl.SMe2.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Samuel E. Neale, Mary F. Mahon, Claire L. McMullin, Andrew S. S. Wilson
Summary: This article investigates the contrasting reactivities of molecular beta-diketiminato (BDI) calcium hydride and n-hexyl derivatives towards bis(pinacolato)diboron (B(2)pin(2)). The study finds that the dimeric calcium hydride forms an unusual diborane(6) dianion, while the initially dimeric organocalcium reagent converts to a calcium diboranate monomer. Attempts to induce heterolysis of the B-B bond in the calcium diboranate monomer were unsuccessful, resulting in either dismutation or the generation of N-donor adduct derivatives. These different reactivities can be explained by density functional theory (DFT) calculations, which attribute them to the larger radius and lower steric congestion of the third-row group 2 cation.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Erika M. Roberts, Fedor M. Miloserdov, Victor Varela-Izquierdo, Mary F. Mahon, Michael K. Whittlesey
Summary: The addition of excess ZnMe2 to a mixture of [Ru(PPh3)(3)HCl] and IMes resulted in the formation of a bis-cyclometallated complex [Ru(IMes)(PPh3)(2)] 2 and a mono-cyclometallated Ru-Zn heterobimetallic complex [Ru(IMes)'(PPh3)(2)(ZnMe)] 3. Further reactions of these complexes with H-2, PhSiH3, pinacolborane, and CO were investigated. Compounds 1, 4, 5, and 6 were synthesized and structurally characterized.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ana M. Geer, Janeth Navarro, Pablo Alaman-Valtierra, Nathan T. Coles, Deborah L. Kays, Cristina Tejel
Summary: Enhancing catalytic activity through synergic effects is a current challenge in homogeneous catalysis. In addition to the well-established metal-metal and metal-ligand cooperation, we showcase an example of self-activation by the substrate in controlling the catalytic activity of a two-coordinate iron complex. This behavior was observed in the regioselective cyclotrimerization of aryl acetylenes. Two kinetically distinct regimes were observed dependent upon the substrate-to-catalyst ratio, showing positive substrate cooperativity.
Editorial Material
Chemistry, Multidisciplinary
Jinxiong Lin, Nathan T. Coles, Manuela Weber, Christian Mueller
Summary: Invited for this month's cover is the group of Prof. Dr. Christian Muller from Freie Universitat Berlin, Germany. The cover picture shows a phosphinine selenide that interacts with organoiodines and halogens to form co-crystalline and charge-transfer adducts. More information can be found in the Research Article by Christian Muller and co-workers.
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Rosalyn L. Falconer, Esme Owen, Michael J. Cowley, John P. Lowe, Claire L. McMullin, Mary F. Mahon, Michael K. Whittlesey
Summary: Treatment of [Ru(L)(PPh3)2(CO)H2] (L = PPh3, IMes) with an N-mesityl amidophosphine aluminium dihydride complex (Al(P-N)H2) gives [Ru(PPh3)2(CO)H3{Al(P-N)H}] (2) and [Ru(IMes)(PPh3)(CO)H3{Al(P-N)H}] (4), which are present in solution as mixtures of diastereomers. Crystal structure determinations and density functional theory (DFT) calculations suggest both 2 and 4 can be formulated as [Ru(L)(PPh3)(CO)H3][Al(P-N)H] complexes with bridging hydride ligands.
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Mary F. Mahon
Summary: This contribution describes the formation of homonuclear sigma bonding between boron mediated by alkaline earth metals. The reaction between alkaline earth bis-(trimethylsilyl)amides and bis(pinacolato)diboron resulted in the formation of group 2 silazide diborane adducts. Further reaction with bis(pinacolato)diboron led to the formation of bis-triboranate derivatives. These complexes provide rare examples of catena-boron species with propagated B-B bonds beyond the common diboranes.
Article
Chemistry, Multidisciplinary
Lea Dettling, Niklas Limberg, Raphaela Kueppers, Daniel Frost, Manuela Weber, Nathan T. Coles, Diego M. Andrada, Christian Mueller
Summary: Trimethylsilyl-substituted triazaphospholes were synthesized via a [3+2] cycloaddition reaction, leading to the formation of unprecedented BF3 adducts of triazaphosphol-5-ylidenes during the attempted isolation of their N-alkylated products. The nature of the carbon(carbene)-boron bond was studied within the DFT framework, revealing strong electron donation from the carbene carbon atom to the boron atom combined with weak back-bonding.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Benjamin L. Morrison
Summary: [{SiNDipp}MgNa](2) reacts directly with H-2 to form a heterobimetallic hydride. Computational density functional theory (DFT) studies suggest that this reactivity is initiated by orbitally-constrained sigma(Mg-Mg)-> sigma*(H-H) and sigma(H-H) -> n*(Na(3s)) interactions between the frontier MOs of both H-2 and the tetrametallic core of [{SiNDipp}MgNa](2).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.
