Article
Chemistry, Inorganic & Nuclear
Enrica Bortolamiol, Giacomo Isetta, Isabella Caligiuri, Nicola Demitri, Stefano Paganelli, Flavio Rizzolio, Thomas Scattolin, Fabiano Visentin
Summary: A general method for synthesizing novel cationic Pd(II) indenyl complexes with one alkyl/aryl phosphine and one N-heterocyclic carbene is reported. The complexes showed high stability in both solid and solution states. These organopalladium compounds have shown promising potential as antiproliferative agents against ovarian cancer cells and as catalysts in Suzuki-Miyaura coupling reactions in aqueous media.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Annaluisa Mariconda, Marco Sirignano, Rubina Troiano, Simona Russo, Pasquale Longo
Summary: This review summarizes the research progress from 2007 to 2022 on the nucleophilic addition of amines and water to terminal and internal alkynes catalyzed by N-heterocyclic carbene gold (I/III) complexes. These reactions are environmentally sustainable and lead to important intermediates in the chemical and pharmaceutical industry.
Article
Chemistry, Inorganic & Nuclear
Thomas Scattolin, Andrea Piccin, Matteo Mauceri, Flavio Rizzolio, Nicola Demitri, Vincenzo Canzonieri, Fabiano Visentin
Summary: Newly synthesized palladium allyl complexes exhibit lower antiproliferative activity, with similar anticancer activity in two ovarian cancer cell lines, suggesting a different mechanism of action compared to platinum-based anticancer drugs. Some compounds show lower cytotoxicity on normal cells and higher selectivity towards cancer cells. Comparing the IC50 values of NHC/PTA complexes and their trifluoromethyl congeners indicates similar antiproliferative activity against cancer cells, but the absence of the CF3 group decreases selectivity towards them.
Article
Chemistry, Physical
Cesar Ruiz-Zambrana, Macarena Poyatos, Eduardo Peris
Summary: A gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NHC) ligand was prepared and its reversible redox properties and catalytic activity in the hydroamination of terminal alkynes were studied.
Article
Chemistry, Inorganic & Nuclear
Roman O. Pankov, Darya O. Prima, Alexander Yu. Kostyukovich, Mikhail E. Minyaev, Valentine P. Ananikov
Summary: Pd/NHC complexes with electron-withdrawing halogen groups were synthesized, and their effect on the Pd-NHC bond was evaluated. The optimized synthetic approach enabled the incorporation of o-, m-, and p-XC6H4-substituted NHC ligands into Pd complexes (X = F, Cl, Br, CF3). The catalytic activity of the obtained Pd/NHC complexes was compared in the Mizoroki-Heck reaction, showing a significant increase in performance for Br and CF3 substituents.
DALTON TRANSACTIONS
(2023)
Article
Multidisciplinary Sciences
Chengtao Yue, Qi Xing, Peng Sun, Zelun Zhao, Hui Lv, Fuwei Li
Summary: The study successfully stabilized palladium in heterogeneous C-C bond formations by developing a novel bifunctional support catalyst, providing new experimental evidence for improving the stability of catalysts and enhancing the efficient applications of supported metal catalysts in advanced synthesis.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Murat Kaloglu, Ismail Ozdemir
Summary: Six novel palladium N-heterocyclic carbene complexes with different ancillary ligands were successfully prepared and used as pre-catalysts in the Buchwald-Hartwig amination reaction. These complexes showed good catalytic activity in the amination of cyclic secondary amines with aryl chlorides, leading to moderate to high yields of N-arylamines under mild reaction conditions.
Article
Chemistry, Inorganic & Nuclear
Xiangyang Xie, Feng Zhang, Huiyu Qin, Xiaoshuang Lu, Bingguang Zhang, Qiaozhen Sun
Summary: A novel macrocyclic bis(N-heterocyclic carbene) precursor was designed and synthesized for the hydrodehalogenation of aryl halides. The synergistic effect of two imida-zoline protons arranged in opposite positions on the macrocycle was found to be closely related to the generation of a small amount of chlorobenzene intermediate product.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Matteo Vanni, Marco Bellini, Silvia Borsacchi, Lucia Calucci, Maria Caporali, Stefano Caporali, Francesco d'Acapito, Marco Geppi, Andrea Giaccherini, Andrea Ienco, Gabriele Manca, Antonio Massimiliano Mio, Giuseppe Nicotra, Werner Oberhauser, Manuel Serrano-Ruiz, Martina Banchelli, Francesco Vizza, Maurizio Peruzzini
Summary: This study provides the first complete structural characterization of 2D BP functionalized with rare discrete Pd-2 units, revealing the existence of interlayer Pd-Pd units and an increase in catalytic activity for the hydrogen evolution reaction. Multiple techniques were utilized to study the morphology of Pd-2/BP nanosheets and to uncover the coordination of Pd-2 units to phosphorus atoms in 2D BP. The presence of Pd-2 units was found to enhance the activity of Pd-2/BP as a catalyst for HER in acidic medium.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Chuting Zhang, Lijuan Peng, Bohou Song, Zhiwen Li, Xiaoqun Cao
Summary: A sustainable catalyst system for Sonogashira cross-coupling reaction was developed using nanoporous palladium as the catalyst. The catalyst remained stable and active over multiple cycles without significant leaching or loss of activity, and high yields of the desired alkynes were obtained.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ming-Tsz Chen, Mu Hsu, Mei-Chen Lin, Yu-Cheng Lien, Kuan-Wei Chen
Summary: The HSAB principle is applied in designing NHC Pd complexes in this study. N-donor ligands as hard bases enhance the catalytic activities of NHC Pd complexes in Suzuki and Buchwald-Hartwig reactions. The Pd complex with tertiary amine ligands exhibits better performance in coupling reactions.
Article
Chemistry, Organic
Aqeel A. Hussein, Azhar Ariffin
Summary: The remote groups in N-heterocyclic carbene (NHC) ligands have a significant influence on metal-catalyzed reactions. The impact of remote steric bulkiness and electronic groups on alkene reactivity and regioselectivity toward hydrocupration is examined using density functional theory calculations. The study also explores the effect of expanded-ring NHCs (ER-NHCs) on the reaction rate.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hyunyong Kim, Hyunseok Kim, Kimoon Kim, Eunsung Lee
Summary: A bottom-up approach to immobilize catalysts into MOFs was reported, resulting in high porosity, stability, and catalytic activity in various reactions. The structures of MOFs bearing metal complexes maintained a similar 4-fold interpenetrated cube, and the high catalytic activity of MOFs can be preserved multiple times without significant loss of crystallinity. Incorporation of various metal complexes into MOFs allows for the preparation of functional MOFs for practical applications.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ceren Akpunar, Namik Ozdemir, Mert Olgun Karatas, Bulent Alici, Ismail Ozdemir
Summary: In this study, we synthesized five new coumarin-functionalised PEPPSI type Pd-NHC complexes to examine their catalyst properties. The complexes showed slightly distorted square-planar geometry and exhibited catalytic activity in the Suzuki-Miyaura reaction of phenylboronic acid and aryl bromide derivatives.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Guoxiang Zhang, Hui He, Xiaoxiao Chen, Shao-Fei Ni, Rong Zeng
Summary: Here, we demonstrate an efficient catalytic system for the intermolecular anti-Markovnikov hydrophosphinylation of olefins using disulfide as a photocatalyst and a hydrogen atom shuttle. This metal-free, base-free, and redox-neutral condition allows alkenes with diverse electronic properties to efficiently proceed with the anti-Markovnikov P-H addition. A plausible mechanism involving the hydrogen atom transfer process between ArS and P(O)-H is proposed.
Article
Chemistry, Inorganic & Nuclear
Chandan Singh, Anuj Kumar, Han Vinh Huynh
INORGANIC CHEMISTRY
(2020)
Review
Chemistry, Multidisciplinary
Han Vinh Huynh
Summary: The Huynh electronic parameter (HEP) is a modern method used to determine ligand donor strengths through (CNMR)-C-13 spectroscopy of metal NHC complexes. It has been applied to classical and organometallic ligands, and extended to HEP2 for measuring bidentate chelators. This review highlights recent applications of HEP and its variants since 2016.
Article
Chemistry, Inorganic & Nuclear
Anuj Kumar, Hemanta K. Kisan, Han Vinh Huynh
Summary: Deprotonation of an N-arylated iminium salt produces a new, unstable acyclic amino carbene (AAC) that can be efficiently trapped at low temperatures with selected elements. Experimental and theoretical studies have shown that this new AAC is a good sigma-donor and pi-acceptor ligand, demonstrating promising electronic properties.
Article
Chemistry, Inorganic & Nuclear
Nemanja Dordevic, Han Vinh Huynh
Summary: Pyrazolin- and indazolin-3-ylidenes, belonging to a less-explored class of NHCs, have been investigated for their electronic properties using NMR spectroscopy. The C-13 NMR chemical shifts were found to be more sensitive in distinguishing structural modifications. By selecting different substituents and benzannulation, slight variations in steric bulk were achieved. The straightforward preparation of air-stable palladium complexes makes these strongly donating NHCs promising for wider applications in organometallic chemistry.
Article
Chemistry, Inorganic & Nuclear
Qiaoqiao Teng, Yaru Zhao, Yuchen Lu, Ziwei Liu, Haiqun Chen, Dan Yuan, Han Vinh Huynh, Qi Meng
Summary: Homo- and heterodicarbene palladium complexes with caffeine-derived N-heterocyclic carbene ligands were synthesized and characterized. The alkylated caffeine-based salts also exhibited superior acidity, allowing the isolation of zwitterionic caffeine monocarbene palladium complexes with outstanding catalytic activity in the cyanation reactions of aryl halides.
Article
Chemistry, Applied
Kausani Ghatak, Han Vinh Huynh
Summary: A library of neutral and cationic palladium complexes of cis-chelating hetero-dicarbene ligands have been prepared and their catalytic activities have been studied. It was found that complexes containing more distinct NHC units exhibited superior catalytic performance.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jia Nuo Leung, Han Vinh Huynh
Summary: A library of 12 palladium(II) complexes, consisting of 10 dithiocarbamato and two xanthato ligands, were synthesized and characterized. The electronic and steric properties of the ligands were evaluated using HEP2 and %Vbur methodologies. The construction of a stereoelectronic map for dithiocarbamates allowed for the identification of optimal ligand parameters for enhanced cytotoxic activities of gold(III) complexes, showcasing the map's usefulness in rational ligand design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Dinh Cao Huan Do, Han Vinh Huynh
Summary: This study attempted to synthesize Pd complexes of different types and found that subtle variations in the N-substituents on the NacAc backbone can affect the chelating mode. Computational studies further confirmed these findings and revealed the impact of different substituents on the energy profiles of the complexes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jia Nuo Leung, Huyen T. T. Luong, Han Vinh Huynh
Summary: In this study, 14 mono-, di-, and tetranuclear palladium complexes were synthesized to investigate the coordination chemistry of symmetrical and unsymmetrical azole-derived diimines and their anions. The obtained complexes exhibit a diverse range of structures and electronic properties imposed by these ligands. The electronic properties of selected bidentate ligands were determined and compared using the monopalladium species, expanding the scope of the HEP2 scale to detect subtle differences. Additionally, the steric bulk of some ligands was estimated using the %V-bur values obtained from the solid-state molecular structures, and a preliminary stereoelectronic map was established.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Han Vinh Huynh, Jia Nuo Leung, Truc Tien Lam
Summary: The donating abilities of anionic ligands X can be easily compared and ranked by C-13 NMR spectroscopy. Downfield shifts of the carbene atom indicate stronger donors, while upfield shifts are observed for weaker ones. This new "HEPx" methodology is demonstrated with 34 anionic X-type ligands.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Dinh Cao Huan Do, Nemanja Dordevic, Han Vinh Huynh
Summary: Attempts to prepare mixed isothiocyanato-bis(imido) Mo-VI complexes led to the discovery of post-metathesis rearrangements towards three distinct products. The construction of the [Mo((NBu)-Bu-t)2(NCS)2] core was ultimately possible in the presence of additional stabilizing donors.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Qiaoqiao Teng, Ziwei Liu, Haobin Song, Jiayu Liu, Yaru Zhao, Weihua Jiang, Han Vinh Huynh, Qi Meng
Summary: Stable cyclopalladated complexes with an (sp(3))C-Pd bond were synthesized by alpha-CH2 deprotonation and palladation of N-alkyl groups of carbene ligands with electron-withdrawing substituents. The strong electron-donating abilities of the resulting (CNHCCsp3)-C-boolean chelators were experimentally confirmed, and the palladacycle underwent template-directed, versatile C-halogenation with X-2.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Qiaoqiao Teng, Ziwei Liu, Haobin Song, Jiayu Liu, Yaru Zhao, Weihua Jiang, Han Vinh Huynh, Qi Meng
Summary: Stable cyclopalladated complexes with (sp(3))C-Pd bond were synthesized via alpha-CH2 deprotonation and palladation of carbene ligands with electron-withdrawing substituents. The strong electron-donating ability of the resulting C-NHC<^>C-sp3 chelators was experimentally confirmed, and the palladacycle underwent versatile C-halogenation with X-2 through template-directed reaction.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhi Hao Toh, Hendrik Tinnermann, Dinh Cao Huan Do, Han Vinh Huynh, Tobias Kramer, Rowan D. Young
Summary: We isolated and characterized the gold(i)-iron(0) adducts and found that the gold-iron interaction is predominantly a sigma-donation from iron to gold. The Pr-i(2)-bimy carbenic C-13 NMR signal can be used to gauge the relative donor strength of Fe(0) donors.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Han Vinh Huynh, Hong Lee Ong, Kausani Ghatak
Summary: The preference for the formation of mono- versus dinuclear mixed carbene/thiolato complexes of Pd-II has been studied. It was found that mononuclear complexes are formed when the sulfur and carbon donors are exclusively cis to each other, while their trans arrangement preferably leads to dinuclear complexes with mu(2)-bridging thiolato ligands. The increased electron density in the latter case cannot be sufficiently compensated by one Pd-II center alone and leads to the formation of dinuclear species with bridging thiolato ligands.
DALTON TRANSACTIONS
(2021)
