Article
Chemistry, Physical
Wen-Yu Lin, Zong-Xian Chen, Haocheng Xiong, Hsien-Chin Li, Yeu-Shiuan Ho, Chi-Tien Hsieh, Qi Lu, Mu-Jeng Cheng
Summary: The electrochemical reduction of CO2 is a promising method for carbon neutrality and utilizing fossil fuels. Advanced catalysts used in CO2ER have shown the ability to generate valuable multi-carbon products through carbon-carbon (C-C) bond formation. However, the coupling of CO2 with *C-1 intermediates has not been explored experimentally or theoretically. This study investigates the possibility of CO2 + *C-1 couplings on Cu(100) surfaces and finds that CO2 can serve as a favorable reagent for C-C bond formation, surpassing the reactivity of *CO under alkaline conditions.
Article
Chemistry, Multidisciplinary
Hong-Tao Zhang, Xiao-Jun Su, Fei Xie, Rong-Zhen Liao, Ming-Tian Zhang
Summary: This study highlights the significance of structure regulation in the O-O bond formation process in binuclear iron catalysts. While some catalysts proceed via oxo-oxo coupling, others with rigid ligands show negligible catalytic activity due to limited isomerization and rotation of Fe=O moieties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Wimonsiri Huadsai, Matthias Westerhausen, Sebastien Bontemps
Summary: The use of Mg and Ca hydride catalysts for the 4e(-) reduction of CO2 is described. Borabicyclo[3.3.1]nonane (9-BBN) and dicyclohexylborane (HBCy2) are used as reductants to generate bis(boryl)acetal compounds, which react with thiol under mild neutral conditions to form borylated hemithioacetal compounds. These compounds can then be converted into dithioacetal compounds through acidic activation or into amino-methyl sulfide compounds through reaction with secondary amine.
Article
Chemistry, Organic
Jiaxing Chen, Yongzhuo Xu, Wen Shao, Jianhua Ji, Boqiang Wang, Muyang Yang, Guojiang Mao, Fuhong Xiao, Guo-Jun Deng
Summary: A Pd-catalyzed C-O cross-coupling reaction was reported, which allows for the synthesis of highly congested hydroxylamines with an α-quaternary carbon center without cleavage of the N-O bond. This strategy shows high chemoselectivity, broad substrate scope, and excellent functional group tolerance, and has been demonstrated by pharmaceutical derivatization and postcatalytic modifications.
Article
Chemistry, Multidisciplinary
Surabhi Chaubey, Pooja Singh, Chandani Singh, Satyam Singh, Sakshi Shreya, Rajesh K. Yadav, Sarita Mishra, Yu-jin Jeong, Bishyajit Kumar Biswas, Tae Wu Kim
Summary: This study reports the synthesis and development of a bamboo-shaped magnesium tetraphenyl porphyrin-based framework photocatalyst for solar light harvesting. The photocatalyst shows high efficiency in direct solar fuel production from CO2 and fine solar chemical synthesis.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Applied
Chunzhe Pei, Jiarui Zong, Bin Li, Baiquan Wang
Summary: The study reports the direct carboxylation of aryl C-H bonds in benzamides catalyzed by nickel under 1 atm of CO2, yielding various products. Detailed mechanistic studies suggest the possible involvement of a Ni(0)-Ni(II)-Ni(I) catalytic cycle in this reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Rui Cao
Summary: This article discusses how tuning the second-sphere environments of Fe porphyrins can improve their activity and selectivity for CO2 reduction.
Article
Chemistry, Multidisciplinary
Yifeng Zhu, Simuck F. Yuk, Jian Zheng, Manh-Thuong Nguyen, Mal-Soon Lee, Janos Szanyi, Libor Kovarik, Zihua Zhu, Mahalingam Balasubramanian, Vassiliki-Alexandra Glezakou, John L. Fulton, Johannes A. Lercher, Roger Rousseau, Oliver Y. Gutierrez
Summary: Research demonstrates that single atoms of Pt-group metals embedded into the surface of Fe3O4 have a stronger interaction with CO2, leading to significantly higher conversion rates compared to nanoparticles. The high activity of single atoms is primarily attributed to the influence of partially oxidic sites.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Hang Li, Na Li, Jinghao Wu, Tianyang Yu, Ran Zhang, Li-Ping Xu, Hao Wei
Summary: In this study, a method for direct insertion of an intramolecular nitrogen atom into an aromatic C-C bond was described. Carbamoyl azides were activated by a Rh catalyst and inserted directly into the C-C bond of an arene ring to produce fused azepine products. The use of a paddlewheel dirhodium complex effectively inhibited the undesired C-H insertion. Density functional theory calculations were used to elucidate the reaction mechanism and chemoselectivity of the Rh-catalyzed reactions. The resulting fused azepine products are highly stable and can be further diversified.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Energy & Fuels
Kai Wang, Lingjie Peng, Xiuli Shao, Qiang Cheng, Juan Wang, Ke Li, Hukun Wang
Summary: In this study, a 2D/2D Nb2O5/g-C3N4 S-scheme heterojunction photocatalyst was successfully fabricated for the photocatalytic CO2 reduction reaction. Under simulated solar irradiation, the optimized sample exhibited 6.7 times and 5.3 times higher total yield of C-1 products (CH4 and CO) compared to pristine Nb2O5 and g-C3N4 nanosheets, respectively, without sacrificial agent or cocatalysts. The improved performance of CO2 photoreduction can be attributed to the unique charge transfer bridge, face-to-face contact, and efficient S-scheme transfer path of photoinduced electron-hole pairs in the heterojunction.
Article
Chemistry, Multidisciplinary
Anthony P. Deziel, Matthew R. Espinosa, Ljiljana Pavlovic, David J. Charboneau, Nilay Hazari, Kathrin H. Hopmann, Brandon Q. Mercado
Summary: The study investigates the insertion of carbon dioxide into a series of metal complexes to generate acetate complexes. It reveals that the insertion of carbon dioxide is facile at room temperature due to the unique ligand, providing valuable insights for carbon dioxide utilization.
Article
Chemistry, Multidisciplinary
Zhiqiang Chen, Aijian Huang, Ke Yu, Tingting Cui, Zewen Zhuang, Shoujie Liu, Jianzhan Li, Renyong Tu, Kaian Sun, Xin Tan, Jiaqi Zhang, Di Liu, Yu Zhang, Peng Jiang, Yuan Pan, Chen Chen, Qing Peng, Yadong Li
Summary: Through a fast-pyrolyzing and controllable-activation strategy, an O-rich carbonaceous support and atomically dispersed FeN4 site with axial O coordination were constructed, achieving a wide potential range and high FECO. DFT calculations revealed that the superior performance originated from the axial O-coordination induced electronic localization enhancement, facilitating CO desorption and increasing the energy barrier for competitive hydrogen evolution reaction.
ENERGY & ENVIRONMENTAL SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Jian Luo, Ai-Qing Zhong, Jia-Hao Qiu, Xiong-Wei Liu, You-Ping Tian, Bao-Hua Zhang, Guo-Shu Chen, Wei Shu, Yun-Lin Liu
Summary: A green and environmentally friendly synthetic approach has been developed for the preparation of racemic or enantioenriched 3,4,6-trisubstituted α-pyrones through a cheap K2CO3-catalyzed C(CO)-C bond insertion reaction of ketenimines with 1,3-diketones. The synthetic utility of this methodology was demonstrated by the broad substrate scope and the concise synthesis of analogues of pharmaceutically active compounds. Furthermore, the study also revealed the potential of extended conjugated α-pyrones for optoelectronic applications in organic light-emitting diodes.
Article
Chemistry, Multidisciplinary
Rajata Kumar Sahoo, Nabin Sarkar, Sharanappa Nembenna
Summary: A new zinc hydride catalyzed partial reduction of heteroallenes via hydroboration, selectively obtaining N-boryl formamide from various isocyanates with different functional groups, indicating potential for chemoselective reduction reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Antonis M. Messinis, Joao C. A. Oliveira, A. Claudia Stueckl, Lutz Ackermann
Summary: A detailed investigation of the C-H activation mechanism with an iron catalyst reveals an unexpected iron(II) alkoxide intermediate, which exhibits higher catalytic activity than previously reported species. Mechanistic studies provide evidence for an oxidative addition reaction and propose the isolated iron(II) alkoxide as a highly reactive precatalyst. These insights form the basis for further developments in iron-catalyzed C-H activation and stereoselective transformations.
Article
Chemistry, Multidisciplinary
Angelica Mejia Fajardo, Nicolas Queyriaux, Aurele Camy, Laure Vendier, Mary Grellier, Iker Del Rosal, Laurent Maron, Sebastien Bontemps
Summary: This study demonstrates the successful activation of the carbonyl function of five different benzaldehyde derivatives using a masked form of OBB intermediate, and the characterization and analysis of the resulting compounds through various experimental methods.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Markus Balmer, Carsten von Haenisch, C. Gunnar Werncke
Summary: The synthesis and characterization of the first homoleptic open-shell transition metal phosphinidenide is presented. Interestingly, the highly reducing phosphinidenide [(sIDipp)P](-) cannot be stabilized in an analogous fashion by coordination to a low-coordinate high-spin iron(ii) center. Through reactions involving [MnL2] and [(sIDipp)PK], the formation process and unexpected observations were documented.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander Reckziegel, Beatrice Battistella, C. Gunnar Werncke
Summary: The synthesis of a T-shaped imido nickel complex is reported, with an unusual shift of a SiMe3 unit observed during the reaction process. The resulting [Ni=NDipp] complex is described as a low-spin nickel(III) imide with limited activity in H-atom abstraction. The reduction of nickel(II) complexes by organic alkali metal salts likely occurs through a direct SET process rather than homolytic Ni-R bond cleavage.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Igor Mueller, C. Gunnar Werncke
Summary: The transformation of alkynes by low-coordinate iron silylamides is examined in this study. It is found that iron complexes can catalyze the cyclotrimerization of diphenyl acetylene and convert terminal alkynes into internal alkynes. Furthermore, a deprotonation/reprotonation mechanism is identified as the key factor in these transformations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Andres Gonzalez, Hannah Gottschling, Carsten von Haenisch, C. Gunnar Werncke
Summary: The behavior of the N-heterocyclic carbene stabilized phosphinidene towards 3d-metal(II) hexamethyldisilazanides was studied. It was found that three-coordinated phosphinidene adducts were formed. These compounds exhibited strong paramagnetism in solution, limiting NMR spectroscopic examinations.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander Reckziegel, Beatrice Battistella, Andreas Schmidt, C. Gunnar Werncke
Summary: In this report, we presented intricate pathways for the synthesis of linear nickel(I) silylamide. The reduction of nickel(II)trisamide with appropriate ligands was explored, leading to the formation of nickel(I) silylamide. The behavior of nickel(II) hexamethyldisilazanide as a source was also investigated. A convenient and reliable synthesis method of nickel(I) silylamide through ligand exchange was proposed.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Christian Schneider, Sergei Ivlev, C. Gunnar Werncke
Summary: A series of different low-coordinate iron selenide complexes are reported, which are obtained by reacting linear iron(I) silylamide with red selenium. By carefully adjusting the reaction conditions, unique low-coordinate iron selenido complexes are formed, including a monoselenide-bridged [2Fe-1Se](2+) complex, as well as mononuclear iron per- and triselenides. Furthermore, C-H bond activation of one of the silylamide ligands by a putative terminal iron monoselenide is observed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sarah Desmons, Yu Zhou, Dan Zhang, Carlos Jarava-Barrera, Anais Coffinet, Antoine Simonneau, Laure Vendier, Gen Luo, Sebastien Bontemps
Summary: The hydroboration of CO2 into bis(boryl)acetal compounds allows for selective reduction of CO2 and subsequent use of the resulting compounds. However, the influence of the boryl moieties on reactivity has not been studied. In this study, different BBA compounds were reacted with 2,6-diisopropylaniline, and significant differences in reaction rates were observed, emphasizing the importance of the boryl moieties. Theoretical investigations revealed the rate-determining step and the main factor driving the reaction rate.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Aurele Camy, Laure Vendier, Christian Bijani, Israel Fernandez, Sebastien Bontemps
Summary: A unique bisphosphine-(NHC-borane) compound was synthesized and its coordination towards gold was studied. The compound supported a bimetallic structure bisphosphine-[NHC-BH3]-(AuCl)(2). The BH3 fragment in the compound was activated upon chloride abstraction from the gold metal center, leading to the formation of a rare Au(4) cluster.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Mihail Atanasov, Serhiy Demeshko, Ting-Yi Chen, Ivan Mohelsky, Eckhard Bill, Milan Orlita, Franc Meyer, Frank Neese, C. Gunnar Werncke
Summary: The magnetic properties of linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] were investigated. Slow-relaxation of magnetization, magnetic hysteresis, and magnetic blocking were observed in K{crypt}[FeL2]. In [KFeL2], with increased axial anisotropy, higher relaxation barrier and blocking temperature were observed, in agreement with field-dependent IR-spectroscopy, magnetic measurements, and theoretical analysis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ramaraj Ayyappan, Koushik Saha, Urminder Kaur, Sourav Gayen, Laure Vendier, Sylviane Sabo-Etienne, Sundargopal Ghosh, Sebastien Bontemps
Summary: The coordination of mbz and mp ligands with a [Ru]-H precursor resulted in the synthesis of two hydrido complexes [RuH(P Cy3)2{x-3-H,H,S-(H)2BH(L)}] (L = mbz (1a), mp (1b)). The reaction of secondary and tertiary silanes with 1a and 1b led to the formation of dihydrido ruthenium(IV) complexes [RuH2(SiPh2R)(PCy3){x-3-H,H,S-(H)2BH(L)}] (R = H, L = mbz (2a), mp (2b); R = Me, L = mbz (2c)) with a coordinated borohydride moiety and a silyl ligand weakly interacting with the ruthenium hydride ligands. NMR investigations and D2 reactivity revealed the exchange between Si-H, Ru-H, and B-H hydride sites.
Article
Chemistry, Inorganic & Nuclear
Andres Gonzalez, Ting-Yi Chen, Serhiy Demeshko, Franc Meyer, C. Gunnar Werncke
Summary: We report the synthesis of a linear N-heterocyclic carbene (NHC)-based chromium(I) silylamide and its magnetic properties. The compound [(IMes)Cr(N{Dipp}SiiPr3)] was obtained through protolytic ligand displacement, and the method was also extended to a bulkier NHC IDipp. Further reactions of the chromium(I) complex yielded different coordination compounds such as a chromium dicarbonyl complex and a chromium bromide complex.
Article
Chemistry, Inorganic & Nuclear
Wimonsiri Huadsai, Matthias Westerhausen, Sebastien Bontemps
Summary: The use of Mg and Ca hydride catalysts for the 4e(-) reduction of CO2 is described. Borabicyclo[3.3.1]nonane (9-BBN) and dicyclohexylborane (HBCy2) are used as reductants to generate bis(boryl)acetal compounds, which react with thiol under mild neutral conditions to form borylated hemithioacetal compounds. These compounds can then be converted into dithioacetal compounds through acidic activation or into amino-methyl sulfide compounds through reaction with secondary amine.
Article
Chemistry, Inorganic & Nuclear
Bahareh Rezaei Kheirkhah, Wimonsiri Huadsai, Phil Liebing, Seibastien Bontemps, Matthias Westerhausen
Summary: Metalation of N-(2,6-dibenzhydryl-4-tolyl)adamantane-1-carboxamide with M(NMe2)4 (M = Ti, Zr, Hf) affords amidate complexes 2 as well as bis(amidate) compounds 3 and 4. In compound 2, the amidate ligand acts as a monodentate base via the oxygen atom with the Ti center. Compounds 3 and 4 contain two bidentate amidate ligands, resulting in hexacoordinate group IV metal atoms.
Article
Chemistry, Multidisciplinary
Sascha Reith, Serhiy Demeshko, Beatrice Battistella, Alexander Reckziegel, Christian Schneider, Andreas Stoy, Crispin Lichtenberg, Franc Meyer, Dominik Munz, C. Gunnar Werncke
Summary: Imidyl and nitrene metal species are important in chemical reactions such as N-functionalisation and aziridination. This article reports on the synthesis and properties of trigonal imido iron complexes, which exhibit different characteristics in their reduced and oxidized forms. Reactivity studies show the ability of these complexes to interact with C-H bonds and other molecules.
