Article
Multidisciplinary Sciences
Guoqi Zhang, Haisu Zeng, Shengping Zheng, Michelle C. Neary, Pavel A. Dub
Summary: The synthesis of branched Markovnikov's alcohols is crucial in the chemical industry. A highly regioselective hydroboration reaction using alkali metal triethylborohydrides as catalysts was discovered. This method allows for the selective and quantitative reduction of asymmetrical epoxides.
Article
Engineering, Environmental
C. Fernandez-Ruiz, S. Liu, J. Bedia, J. J. Rodriguez, L. M. Gomez-Sainero
Summary: The bimetallic catalyst AgPdCl/C showed higher selectivity to ethylene and propylene, while AgPdN/C exhibited higher selectivity to paraffins. The small Pd nanoparticles in AgPdCl/C acted as active sites for converting chloromethanes into light unsaturated hydrocarbons, leading to improved performance in terms of selectivity to olefins. AgPdCl/C also showed high stability and selectivity in the hydrodechlorination of trichloromethane.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2021)
Article
Polymer Science
Jinxin Nie, Feiyang Ren, Zhen Li, Kun Tian, Hui Zou, Xiaohua Hou
Summary: Several binuclear vanadium complexes were synthesized and investigated as catalysts for ethylene (co)polymerization. The binuclear complexes exhibited higher activities than the mononuclear analogues in ethylene polymerization and showed moderate activity in copolymerization with polar vinyl monomers.
Article
Chemistry, Multidisciplinary
Xue Zhao, Manussada Ratanasak, Jun-ya Hasegawa, Kazumasa Kon, Kazuaki Ishihara
Summary: This study developed magnesium(ii) and sodium(i) complexes derived from BHT-H and PBTP-H-2 as catalysts for the transesterification of MA and MMA. The Mg(PBTP) and Na-2(PBTP) catalysts were found to be 41 and 81 times more effective than Mg(BHT)(2) and Na(BHT), respectively. These catalysts showed high efficiency across a range of alcohols.
Article
Chemistry, Multidisciplinary
Saurav Bhattacharya, Andrea Barba-Bon, Tsedenia A. Zewdie, Anja B. Mueller, Talha Nisar, Anna Chmielnicka, Iwona A. Rutkowska, Christian J. Schuermann, Veit Wagner, Nikolai Kuhnert, Pawel J. Kulesza, Werner M. Nau, Ulrich Kortz
Summary: We report the discovery of the first two cationic palladium(II)-oxo clusters (POCs) containing f-metal ions, and investigate their physicochemical characterization. The molecular structure of these novel POCs consists of an octahedral {Pd6O12} core capped by eight M-IV ions, forming a cationic, cubic assembly {Pd6O12M8IV}. We also found that these POCs can form host-guest inclusion complexes with 4-sulfocalix[n]arenes, and can be used as pre-catalysts for electrocatalytic CO2 reduction and HCOOH oxidation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Ntombizonke P. Ngubane, Saphan O. Akiri, Bernard Omondi, Stephen O. Ojwach
Summary: This article reports the synthesis of a series of complexes [Pd(L1)2] (Pd1), [Pd(L2)2] (Pd2), [Pd(L3)2] (Pd3), [Pd(L4)2] (Pd4), [Pd(L5)2] (Pd5) and [Pd(L6)2] (Pd6) using Pd(OAc)2 as the precursor. The characterization of chemical structures and catalytic performances of these complexes revealed their excellent catalytic activity and selectivity in the methoxycarbonylation of olefins.
Article
Chemistry, Physical
Sichen Liu, Carlos Fernandez-Ruiz, Ana Iglesias-Juez, Maria Martin-Martinez, Jorge Bedia, Carlo Marini, Giovanni Agostini, Juan Jose Rodriguez, Luisa Maria Gomez-Sainero
Summary: This study investigates the upgrading of wasted chloroform for the production of olefins using different catalysts prepared with different precursors. The results show that PdCl-based catalysts demonstrate electron transfer from the support to Pd nanoparticles, which is not observed in PdN-based catalysts. The catalyst with the smallest and well-dispersed Pd nanoparticles on CNT exhibits the highest activity and selectivity to olefins, while the other catalysts suffer from lower selectivity and activity due to the formation of Pd carbides on larger Pd nanoparticles.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Multidisciplinary Sciences
Eiji Kudo, Kota Sasaki, Shiori Kawamata, Koji Yamamoto, Tetsuro Murahashi
Summary: The authors describe a method for selective isomerization of E-1,3-dienes to Z-isomers without photoirradiation using a dinuclear Pd(I)-Pd(I) complex, achieving kinetic trapping through rational sequences of reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Patrick Sand, Bernd Schmidt
Summary: The regioselectivity of two mechanistically distinct alkenylation reactions catalyzed by in situ-formed cationic transition metal complexes was studied using N-allyl-N-phenylethenesulfonamide as a model compound. Orthogonal selectivity was observed for the Ru-catalyzed C-H-activating alkenylation with acetanilides, which occurs preferentially at the electron deficient double bond, and for a Pd-catalyzed Heck-type coupling with arene diazonium salts, which occurs preferentially at the more electron rich double bond of the N-allyl substituent.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ye Liu, Shi-Huan Li, Shi-Yu Chen, Xiao-Bing Lu
Summary: In this study, propylene was successfully incorporated into an ethylene/CO copolymer chain using a cost-effective nickel catalyst. The electronic and steric effect of different moieties in the catalyst was systematically investigated for terpolymerization. It was observed that the melting temperature (Tm) of the resulting polyketones was proportional to the amount of propylene incorporated into the polymer chain, without significant impact on the degradation temperature. The PNPO catalysts showed higher preference for propylene consumption compared to dppp-type catalysts, which is important for efficient utilization of alpha-olefin resources.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Reike Clauss, Saral Baweja, Dmitri Gelman, Evamarie Hey-Hawkins
Summary: A series of novel heterobimetallic Pd-II/M-II complexes were synthesized and exhibited a cooperative effect in catalyzing coupling reactions, leading to improved catalytic activity and selectivity for the formation of various Z-alkenes. The homogeneous nature of the catalytically active species was also demonstrated in the study.
DALTON TRANSACTIONS
(2022)
Article
Polymer Science
Wenbo Du, Handou Zheng, Yinwu Li, Chi Shing Cheung, Donghui Li, Heng Gao, Huiyun Deng, Haiyang Gao
Summary: This study developed a new neutral nickel catalyst with good thermal stability and high tolerance towards polar monomers. The copolymerization reaction using this catalyst produced branched copolymers with high molecular weight and high monomer incorporation, similar to commercially prepared products. Density functional theory calculations provided insights into the mechanism of copolymer formation.
Article
Chemistry, Inorganic & Nuclear
Catriona R. Vanston, Thomas P. Nicholls, Alex C. Bissember, Michael G. Gardiner, Curtis C. Ho
Summary: This study prepared palladium complexes with a new class of cationic aNHC ligands, but found that greater conformational restrictions are necessary to achieve significant electron transfer.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Malgorzata Bolt, Lionel Delaude, Patrycja Zak
Summary: In this study, eight rhodium complexes were prepared and found to be catalytically active in the hydrothiolation of terminal alkynes. The steric bulk of the carbene was found to significantly affect the reaction rate and selectivity. The experimental conditions were optimized to enable efficient synthesis of α-vinyl sulfides with high atom economy and low catalyst loading.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Babak Tahmouresilerd, Dawei Xiao, Loi H. Do
Summary: In this study, two nickel complexes with conformationally rigid bisphosphine mono-oxide ligands were synthesized, showing competent catalytic activities for ethylene homopolymerization and copolymerization. The addition of Li+ to one of the complexes led to a significant enhancement in catalyst activity and polar monomer incorporation, making the nickel-alkali catalysts competitive with other efficient Ni-based systems for ethylene and methyl acrylate copolymerization.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Maria Perez-Iglesias, Rebeca Infante, Juan A. Casares, Pablo Espinet
Article
Chemistry, Organic
Vanesa Salamanca, Ana C. Albeniz
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Alberto Toledo, Vanesa Salamanca, Teresa Perez-Moro, Ana C. Albeniz
Summary: The transmetalation of acyclic monoamino and alkoxo carbenes from tungsten to group 11 metals has been studied, showing that gold carbenes can be isolated easily while copper carbenes can be detected, but no experimental evidence of silver carbenes formation was found. The electrophilic character of copper and gold carbenes is supported by hydrolysis products, while silver shows unexpected nucleophilic behavior due to energetically accessible protonation of a cationic silver carbene.
Article
Chemistry, Applied
Francisco Villalba, Ana C. Albeniz
Summary: The pyridone fragment in the ligand plays a crucial role in the C-H activation step of the oxidative Heck reaction. The presence of bipy-6-OH is required for the alkenylation of low acidity fluoroarenes, while it is detrimental for high acidity fluoroarenes. The use of catalytic amount of sodium molybdate as a base is optimal in all these reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Editorial Material
Chemistry, Inorganic & Nuclear
Cyril Godard, Carmen Claver, Ana C. Albeniz
Summary: Supported catalysts offer both the activity of molecular catalysts and the convenience and reusability of catalysts in a difference phase. With continuous solutions to common problems such as leaching, supported catalysts are becoming increasingly viable for applied research.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ignacio Perez-Ortega, Ana C. Albeniz
Summary: A new polynorbornene skeleton has been discovered, synthesized using a nickel catalyst and controlled ligand coordination ability. The backbone structure is formed through vinylic addition polymerization and β-C elimination, and can be modulated by ligand coordination.
Editorial Material
Chemistry, Inorganic & Nuclear
Ana C. Albeniz
Summary: The article introduces the Specialized Group of Organometallic Chemistry within the Spanish Royal Society of Chemistry and its achievements in the field of organometallic chemistry. It also presents the RSEQ-GEQO Prizewinners Special Collection of EurJIC.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ignacio Perez-Ortega, Ana C. Albeniz
Summary: The reaction between [NiArBr(PPh3)(2)] and AgBF4 results in the abstraction of halide and phosphine from the nickel center by silver. The reaction in CH2Cl2/toluene solvent forms cationic aquo derivatives [NiAr(H2O)(PPh3)(2)]BF4 and [NiAr(H2O)(2)(PPh3)]BF4, while in acetone solvent, it forms a complex [NiAr(kappa(2)-O, O-MeC(O)CH2C(OH)Me-2)(PPh3)] with a chelating ligand formed by the aldol self-condensation of acetone. Phosphine abstraction by silver is less favorable for palladium(ii) complexes and only occurs under certain conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Cintya Pinilla, Vanesa Salamanca, Agusti Lledos, Ana C. Albeniz
Summary: Metal-catalyzed C-H functionalizations on the aryl ring of anilines usually require cumbersome N-protection-deprotection strategies for chemoselectivity. In this study, we demonstrate a Pd-catalyzed direct C-H arylation of unprotected anilines with no competition from N-arylation product. The ligand [2,2'-bipyridin]-6(1H)-one drives the chemoselectivity by kinetic differentiation in the product-forming step while aiding in the C-H cleavage step. The deprotonation of the NH moiety in an anionic intermediate favors regioselectivity towards ortho substitution.
Article
Chemistry, Inorganic & Nuclear
Francisco Villalba, Ana C. Albeniz
Summary: Hydrazones play a crucial role as ligands in palladium-catalyzed cross coupling reactions, but their interaction with palladium and reaction mechanism remain understudied.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Francisco Villalba, Ana C. Albeniz
Summary: The reactions of Pd-aryl complexes with diazo compounds N2CH-CH=CHPh and N2CHPh were studied, and it was found that the migratory insertion of a non-stabilized CHR carbene into the Pd-aryl bond led to the formation of eta(3)-allylic and eta(3)-benzylic palladium complexes. This provides compelling experimental evidence for the key step in the palladium-catalyzed cascade transformations of diazo derivatives.
DALTON TRANSACTIONS
(2022)
Article
Polymer Science
Ignacio Perez-Ortega, Ana C. Albeniz
Summary: This study successfully incorporates functional groups in the skeleton of vinylic addition polynorbornenes using specific catalysts. The copolymers with different compositions and molecular weights can be synthesized by employing different catalysts.
Article
Polymer Science
Ignacio Perez-Ortega, Ana C. Albeniz
Summary: In this study, it was found that benzylic palladium complexes are suitable precatalysts for the challenging vinylic addition polymerization of 5-vinyl-2-norbornene (VNB). A highly active catalyst can be formed with a mixture of [Pd-2(mu-Br)(2)(eta(3)-C6H5CHCH2C6F5)(2)], PCy3 and NaBAr4F, resulting in high molecular weight polymers of VNB with preserved exocyclic pendant double bonds. The nature of the counterion, with BAr4F- being the most efficient among several tested, plays a crucial role in the propagation of the polymerization process.
Article
Chemistry, Organic
Vanesa Salamanca, Ana C. Albeniz
Summary: Functionalization of simple arenes is challenging, as it requires cleaving the sluggish C-H bond and overcoming the weak coordinating ability of the arene pi-system. Using a well-defined palladium complex with a specific ligand and a moderately coordinating solvent can decrease the amount of arene used, while a co-solvent like t-butyl methyl ketone can accelerate the reaction process by altering the concentration and stability of relevant metal species.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Inorganic & Nuclear
J. Emilio Exposito, Gabriel Aullon, Manuel Bardaji, Jesus A. Miguel, Pablo Espinet
DALTON TRANSACTIONS
(2020)