Article
Chemistry, Multidisciplinary
Eric S. Yang, Emma Combey, Jose M. Goicoechea
Summary: This article reports a series of group 9 pyridine-diimine complexes M((PDI)-P-Dipp)X and [M((PDI)-P-Dipp)L](+) (M = Co, Rh; (PDI)-P-Dipp = 1,1'-(pyridine-2,6-diyl)bis(N-(2,6-diisopropylphenyl)ethan-1-imine); X = CP-, CCH-; L = CO, tBuNC) with strong-field ligands, including the cyaphide ion (C=P). A comparative study of the group 9 PDI cyaphide complexes Co((PDI)-P-Dipp)(CP) and Rh((PDI)-P-Dipp)(CP), as well as the N-heterocyclic carbene (NHC) gold(I) cyaphide complex Au(IDipp)(CP) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), reveals the s donor and p acceptor properties of the kC-cyaphido ligand, and suggests a position for this ion in the spectrochemical series.
Article
Chemistry, Multidisciplinary
Diego Sorbelli, Leonardo Belpassi, Paola Belanzoni
Summary: This work systematically studied the electronic structure and reactivity of Au-Al complexes with different aluminyl scaffolds, comparing them to carbene analogues. The results reveal that aluminyls and carbenes exhibit different behavior when bound to gold, with aluminyls forming an electron-sharing and weakly polarized Au-Al bond. The poor modulability of their electronic structure and bond nature is reflected in the similar reaction mechanisms of gold-aluminyl complexes towards CO2.
Article
Chemistry, Multidisciplinary
Estefan van Vuuren, Frederick P. Malan, Marile Landman
Summary: Novel Ir-based NHC complexes (1-4) were synthesized using N-alkenyl functionalized imidazolium salts with Ir(iii) precursors. Complex 1 represents an unprecedented cyclometallated complex, which is the first and only example in literature, to our knowledge, of a non-aromatic C(sp(2))-H activation leading to a C(sp(3))-Ir cyclometallated product. Subsequent reactions with a range of imidazolium salts featuring different N-pendant arms were performed, including alkenyl and benzyl tethers. Selectivity with regards to cyclometallation behavior of the iridium center was observed in preference for a benzyl cyclometallated product over alkenyl cyclometallation. Benzyl-containing products proved most promising as active catalysts in both the hydrosilylation of internal alkynes with a conversion of up to 59% after 1 hour, as well as the transfer hydrogenation of ketone and aldehyde substrates with conversions of up to 100% after 18 hours using catalyst loadings of 4 and 1 mol% respectively.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Suman K. Barman, Meng-Yin Yang, Trenton H. Parsell, Michael T. Green, A. S. Borovik
Summary: This study explores the mechanism of metal-oxido species in C-H bond cleavage, highlighting the importance of basicity in achieving enzymatic function. The research found that proton transfer plays a more dominant role than electron transfer in these reactions.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Multidisciplinary
Greggory T. Kent, Xiaojuan Yu, Guang Wu, Jochen Autschbach, Trevor W. Hayton
Summary: The reaction of AnCl(NR2)3 with lithiated 3,3-diphenylcyclopropene forms new compounds, and analysis reveals the molecular structure, reaction mechanism, and bonding characteristics involving actinide elements.
Article
Chemistry, Inorganic & Nuclear
Alexandros Mortis, Cacilia Maichle-Mossmer, Reiner Anwander
Summary: A series of new yttrium donor adduct complexes were successfully synthesized and fully characterized, with two chosen for surface organometallic chemistry research. Mesoporous nanoparticles were used as a support material, with various characterization techniques employed to analyze the parent and hybrid materials, showing that surface silylation promoted by HN(SiHMe2)(2) is superior to titration with lithium alkyl LiCH2SiMe3.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yun Xiong, Shicheng Dong, Shenglai Yao, Chenshu Dai, Jun Zhu, Sebastian Kemper, Matthias Driess
Summary: White phosphorus (P-4) undergoes degradation to produce 2,5-disila-3,4-diphosphapyrrole 2 and two novel functionalized Si=P doubly bonded compounds 3 and 4 when exposed to the new N,N-bis(silylenyl)aniline PhNSi2 1. The transformation of compound 2 into compounds 3 and 4 can be achieved depending on the molar ratio of 1 and P-4 as well as the reaction conditions. These compounds can interconvert through reactions with 1 and P-4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kento Shimamoto, Yusuke Sunada
Summary: The denitrogenative reductive coupling of CNtBu to afford a disilylketenimine with an azadisilacyclobutane skeleton was achieved on a multinuclear silylene-bridged Ni cluster framework. This reaction provides a new strategy for the efficient synthesis of organic compounds without the use of strong reducing reagents.
Article
Chemistry, Inorganic & Nuclear
Fangjun Zhang, Keyu Han, Jiamin Cai, Zihao Ye, Jie Zhang, Xigeng Zhou, Zhiming Li
Summary: Rare-earth metal dialkyl complexes can be used to functionalize P-4, resulting in the formation of rare-earth polyphosphorus complexes and organophosphorus compounds. A series of experiments were conducted to achieve atom-economic conversion of P-4, and the new compounds were characterized.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mannem Adi Narayana, Moulali Vaddamanu, Arruri Sathyanarayana, Kumar Siddhant, Shohei Sugiyama, Kazuhisa Ozaki, Aravind Kumar Rengan, Kavitha Velappan, Kyohei Hisano, Osamu Tsutsumi, Ganesan Prabusankar
Summary: This study investigated a mesoionic N-heterocyclic carbene-gold(i) complex with a unique intramolecular hydrogen bonding interaction, revealing the structure and favored gold-hydrogen bonding situation of the complex. The photophysical properties of the gold(i) complex were also explored.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Kai-Stephan Feichtner, Lennart T. Scharf, Thorsten Scherpf, Bert Mallick, Nils Boysen, Viktoria H. Gessner
Summary: The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P-H bonds has been reported. These complexes exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Additionally, deuteration experiments and computational studies have shown that cyclometallation is initiated at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Vivek Gupta, Sadhana Singh, Sharad Kumar Sachan, BrijKishor Maurya, Subhamoy Char, Dasari L. V. K. Prasad, Ganapathi Anantharaman
Summary: This study investigates the reaction properties and products of acyclic palladium amidine chloride under different conditions. It is found that cyclic six-membered (triazapentadiene)palladium complexes can be obtained by reacting palladium complexes or formamidinium salts with acetonitrile, but different products are obtained with acetonitrile or acrylonitrile.
INORGANIC CHEMISTRY
(2022)
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, Organic
Lucas Vidal, Pan -Pan Chen, Eva Nicolas, Andrew Hackett, Craig M. Robertson, Kendall N. Houk, Christophe Aissa
Summary: The iridium-catalyzed intramolecular cyclopropanation of alpha-carbonyl sulfoxonium ylides (SY) in the presence of a chiral diene is reported with high yield (up to 96%) and enantioselectivity (98%). Density functional theory calculations suggest that the re face of the olefin prefers to attack an iridium carbene intermediate in an asynchronous concerted step independent of the geometry of the olefin.
Article
Chemistry, Multidisciplinary
Philip M. Keil, Terrance J. Hadlington
Summary: A novel class of non-innocent ligands, cationic single-centre ambiphiles, is introduced through phosphine-functionalised cationic tetrylene Ni-0 complexes. The combination of the electronic nature of low-coordinate tetryliumylidenes and the geometrically constrained chelating phosphine arm leads to strongly electrophilic E-II centres that readily bind nucleophiles. This discovery opens up possibilities for the development of multi-talented ligands in cationic single-centre ambiphiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jian Xu, Sudip Pan, Shenglai Yao, Gernot Frenking, Matthias Driess
Summary: The stable plumbylone {[Si-II(Xant)Si-II]Pb-0} 3 and its isolable carbonyl iron complex {[Si-II(Xant)Si-II](PbFe)-Fe-0(CO)(4)} 4 were obtained by reduction reactions. While compound 4 showed relatively good stability, it decomposed to elemental Pb and {[Si-II(Xant)Si-II]Fe(CO)(3)} 5 at higher temperatures. Reaction of 4 with [Rh(CO)(2)Cl](2) yielded the unusual dimeric [(OC)(2)RhPb(Cl)Fe(CO)(4)] complex 6 with Rh-Pb-Fe bonds. The molecular and electronic structures of 3 and 4 were determined by Density Functional Theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yun Xiong, Shicheng Dong, Shenglai Yao, Chenshu Dai, Jun Zhu, Sebastian Kemper, Matthias Driess
Summary: White phosphorus (P-4) undergoes degradation to produce 2,5-disila-3,4-diphosphapyrrole 2 and two novel functionalized Si=P doubly bonded compounds 3 and 4 when exposed to the new N,N-bis(silylenyl)aniline PhNSi2 1. The transformation of compound 2 into compounds 3 and 4 can be achieved depending on the molar ratio of 1 and P-4 as well as the reaction conditions. These compounds can interconvert through reactions with 1 and P-4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
J. Niklas Hausmann, Stefan Mebs, Holger Dau, Matthias Driess, Prashanth W. Menezes
Summary: In this study, a layered cobalt borophosphate precursor is reconstructed into two different cobalt oxyhydroxide phases, and the electrocatalytic properties of various cobalt oxyhydroxides and phosphate derivatives are compared. The choice of buffer, the number of edge sites not inhibited by buffers, and the morphology are identified as important factors affecting the oxygen evolution reaction activity.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Physical
Jan Niklas Hausmann, Pramod Menezes, Gonela Vijaykumar, Konstantin Laun, Thomas Diemant, Ingo Zebger, Timo Jacob, Matthias Driess, Prashanth W. Menezes
Summary: This article reports a new method of growing hierarchical nanostructures on nickel foam, and successfully doped iron element for oxidation reactions and oxygen evolution reaction. The results show that iron doping is more suitable for oxidation reactions, which can generate higher current density and Faradaic efficiency. In the oxygen evolution reaction, the iron-doped nickel foam electrode can achieve the current density required by industry and maintain stable performance. This article reveals the effects of iron doping and its impact on the reaction mechanism.
ADVANCED ENERGY MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Shenglai Yao, Artetuis Saddington, Yun Xiong, Matthias Driess
Summary: In this study, a series of compounds containing low-valent central atoms were successfully synthesized using bis(NHSi) ligands with electronically and spatially different spacers. The chemical reactions and electronic structures of these compounds were investigated. By controlling the Si–Si distance, a variety of low-valent compounds of Si, Ge, and Sn elements were synthesized, and the o-carborane-based bis(NHSi) ligand enabled the oxidation of Si and Ge as well as the isolation of new compounds. Furthermore, future research directions were proposed, such as applying bis(NHSi) ligands to other main-group elements and developing acyclic silylene ligands.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Physical
Lukas Reith, Jan Niklas Hausmann, Stefan Mebs, Indranil Mondal, Holger Dau, Matthias Driess, Prashanth W. W. Menezes
Summary: The redox behavior and active structure of cobalt-iron oxyhydroxides catalysts for the oxygen evolution reaction (OER) are investigated. Quasi in situ X-ray absorption spectroscopy is used to track the redox behavior and identify the active structure, and it is found that iron exhibits substantial redox behavior with an average oxidation state between 2.8 and above 3.2. The contraction of the Fe-O bond length and distortion of the [MO6] octahedra during OER suggest the presence of oxyl radicals and the involvement of di-mu-oxyl radical bridged cobalt-iron centers as the active sites. These findings contribute to the understanding of bimetallic iron-containing OER catalysts.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Hongyuan Yang, Gonela Vijaykumar, Ziliang Chen, J. Niklas Hausmann, Indranil Mondal, Suptish Ghosh, Victor C. J. Nicolaus, Konstantin Laun, Ingo Zebger, Matthias Driess, Prashanth W. Menezes
Summary: A well-defined helical iron borophosphate (LiFeBPO) is developed as an electro(pre)catalyst for the oxygen evolution reaction (OER) and selective alcohol oxidation. This catalyst exhibits exceptional OER performance and high selectivity for alcohol electrooxidation. In-situ and ex situ investigations reveal a deep reconstruction of LiFeBPO during OER, forming a 3D open porous skeleton assembled by ultrasmall, low-crystalline alpha-FeOOH nanoparticles.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Philip M. Keil, Ademola Soyemi, Kilian Weisser, Tibor Szilvasi, Christian Limberg, Terrance J. Hadlington
Summary: The open-shell cationic stannylene-iron(0) complex 4 can cooperatively and reversibly cleave dihydrogen at the Sn-Fe interface under mild conditions. The one-electron reduction of the related Ge-II-Fe-0 complex 3 leads to oxidative addition, forming Fe-I phosphide species 7. The covalently bound tin(II)-iron(-I) compound 8 has been characterized and shows high localization of electron spin density at Fe-I in this unique d(9)-iron complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Annika Schulz, Till L. Kalkuhl, Philip M. Keil, Terrance J. Hadlington
Summary: We report a facile synthetic method for accessing rare T-shaped Ni-0 species stabilised by low-coordinate cationic germylene and stannylene ligands which behave as Z-type ligands towards Ni-0. The geometry switch at Ni-0 from T-shaped to trigonal planar, due to the in situ modulation of ligand electronics, has a significant impact on catalysis. The T-shaped complexes show high catalytic activity in the hydrogenation of alkenes under mild conditions, while the trigonal planar and tetrahedral Ni-0 complexes with L-type chloro- or cationic-tetrylene ligands are inactive.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Changkai Shan, Shicheng Dong, Shenglai Yao, Jun Zhu, Matthias Driess
Summary: We report the successful synthesis and unique reactivity of the first divalent silicon species 3 supported by a chelating bis(N-heterocyclic silylene)bipyridine ligand. The compound was obtained by direct reaction of 1 with Idipp-SiI2 or by two-electron reduction of the corresponding Si(IV) precursor 2. Density functional theory calculations reveal that the lone pair on the ptSi(II) resides almost entirely in its 3pz orbital, distinguishing it from known four-coordinate silylenes. The reaction of 2 with [CuOtBu] leads to the regeneration of the bis(silylene) arms and the oxidation of the central Si(II) atom, forming the neutral bis(silylene)silyl Cu(I) complex 5.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Michael Schwarze, Steffen Borchardt, Marvin L. L. Frisch, Jason Collis, Carsten Walter, Prashanth W. W. Menezes, Peter Strasser, Matthias Driess, Minoo Tasbihi
Summary: Four commercial titanium dioxide photocatalysts were immobilized on steel plates and their performance in phenol degradation under UV-LED irradiation was investigated. The best result was obtained with the P90/UV/H2O2 system, achieving 100% degradation and around 70% mineralization after 3 hours of irradiation. The study highlights the importance of water quality for the photocatalytic performance.
Article
Chemistry, Multidisciplinary
Indranil Mondal, Pramod V. Menezes, Konstantin Laun, Thomas Diemant, Mohammad Al-Shakran, Ingo Zebger, Timo Jacob, Matthias Driess, Prashanth W. Menezes
Summary: A hierarchical amorphous birnessite-type manganese oxide layer was synthesized on 3D nickel foam using a rapid in-liquid plasma approach. The resulting catalyst exhibited high activity in oxygen evolution reaction (OER) and chemoselective dehydrogenation of benzylamine.
Review
Nanoscience & Nanotechnology
Suptish Ghosh, Basundhara Dasgupta, Carsten Walter, Prashanth W. Menezes, Matthias Driess
Summary: The ongoing challenge of developing efficient electrocatalysts for water-splitting has led to intense efforts in designing effective methods to improve electrocatalytic performances. The use of single-source (molecular) precursors (SSPs) has gained significant attention for their ability to create nanostructured materials with fine-tuned properties, resulting in high and stable catalytic activities.
Article
Chemistry, Multidisciplinary
Till L. Kalkuhl, Lei Qin, Lili Zhao, Gernot Frenking, Terrance J. Hadlington
Summary: Stable sigma-complexes of a 1,2-dichlorodigallane derivative with Ni and Pd were reported in this study, and in-depth computational analysis revealed considerable Ga-Ga bonding interactions. The controlled disproportionation of the Ni complex led to a novel GaI-nickel species.
