Article
Chemistry, Multidisciplinary
Miquel Navarro, Juan Miranda-Pizarro, Juan J. Moreno, Carlos Navarro-Gilabert, Israel Fernandez, Jesus Campos
Summary: In this study, the first dicoordinate gold(i)-ethylene adduct was isolated and characterized using a bulky tris-2-(4,4 '-di-tert-butylbiphenylyl)phosphine ligand. Density Functional Theory (DFT) calculations showed that pi-backdonation plays a minor role in its bonding situation compared to tricoordinate analogues.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Wenqing Zhang, Xiaoquan Feng, Yan Zhou, Jing-Huo Chen, Seik Weng Ng, Guang Yang
Summary: Four silver(I) pyrazolato complexes were synthesized and characterized, and their structural transformations were investigated through experimental and theoretical analyses. The study provides insights into the solvent-assisted, acid-base interaction promoted, and thermodynamically favored process of isomeric transformation.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Inorganic & Nuclear
Masahiko Maekawa, Terumasa Hayashi, Kunihisa Sugimoto, Takashi Okubo, Takayoshi Kuroda-Sowa
Summary: The crystal structures of Cu(I)-C2H4 complexes with different ligands and reaction conditions have been determined. Among them, the coordination polymer 4 bridged by unusual mu-eta(2):eta(2)-C2H4 and mu-BF4- has particular significance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Adway O. Zacharias, James X. Mao, Kwangho Nam, H. V. Rasika Dias
Summary: This study synthesized and studied the structures and interactions of vinyltrifluoroborate ligands in metal complexes, revealing asymmetric binding between metal and carbon, as well as the influence of supporting ligands on the binding between ligands and metals.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
David Vesseur, Karinne Miqueu, Didier Bourissou
Summary: A mono-substituted Au(I) carbene was synthesized by reacting HC(N-2)(Dmp) (Dmp = 2,6-dimesitylphenyl) with an (o-carboranyl)-diphosphine AuNTf2 complex. It exhibited stability up to about 10 degrees C and its structure was determined using NMR spectroscopy. Density functional theory calculations revealed that the chelating P<^>P ligand enhanced Au -> C-carb backdonation, while the Dmp substituent provided kinetic stabilization without altering the electronic structure of the carbene complex.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Gyeongjin Park, Francois P. Gabbai
Summary: This study focuses on the hydrogen bonding interaction between a metallobasic gold(I) center and an OH functionality, demonstrating the authentic interaction between them. Moreover, experimental results suggest that increasing the acidity of the OH functionality may not necessarily enhance the stability of the Au(I)···H-O interaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Beenish J. Azhar, Safdar Abbas, Sitwat Aman, Maria Yamburenko, Wei Chen, Lena Mueller, Buket Uzun, David A. Jewell, Jian Dong, Samina N. Shakeel, Georg Groth, Brad M. Binder, Gevorg Grigoryan, Eric Schaller
Summary: The gaseous hormone ethylene is perceived in plants by membrane-bound receptors, with ETR1 from Arabidopsis being the most well-studied receptor. An Asp residue within the ETR1 transmembrane domain is found to play a critical role in ethylene binding. Mutating the Asp to Asn results in a functional receptor with reduced affinity for ethylene, but it still mediates ethylene responses in plants. This study proposes a new structural model for the mechanism of ethylene binding and signal transduction, which shares similarities with a mammalian olfactory receptor.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Physical
Miquel Navarro, Macarena G. Alferez, Morgane de Sousa, Juan Miranda-Pizarro, Jesus Campos
Summary: A series of gold(I)-ethylene pi-complexes containing bulky phosphine ligands have been synthesized, and the importance of these ligands in stabilizing the gold(I)-ethylene bond and preventing decomposition has been discovered. By improving the catalyst structure and reaction conditions, the catalytic performance in the hydroamination of ethylene can be enhanced.
Article
Chemistry, Inorganic & Nuclear
Rebecca Schneider, Tobias A. Engesser, Jessica N. Hamann, Christian Nather, Felix Tuczek
Summary: In this study, four structurally related bis-tridentate N-donor ligands with different functionalities were synthesized to form corresponding dicopper(I) complexes as catalysts for the conversion of 2,4-di-tert-butylphenol. The results showed evidence of a mu-eta(2):eta(2)-peroxo-dicopper(II) species and catalytic conversion in the imine ligand systems but not in the amine ligand systems.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Guillermo Romo-Islas, Jas S. Ward, Kari Rissanen, Laura Rodriguez
Summary: The use of heterometallic Au/Cu systems with metallophilic contacts is ideal for obtaining red phosphorescent materials. The synthesized compounds have an ionic character due to the reaction of gold-(I) complexes with copper-(I) salts, and the counterion affects the emission wavelength. These compounds have been tested as photosensitizers for generating singlet oxygen.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Neda Heydari, Rahman Bikas, Milosz Siczek, Tadeusz Lis
Summary: A Cu(II) complex [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH (1) was synthesized by reacting Cu(NO3)2middot3H2O with H2L in methanol solvent. The structure of [Cu(HL)(NO3)(CH3OH)]middotCH(3)OH was determined by single-crystal X-ray analysis, showing that it is a mononuclear Cu(II) complex with a free NH2 functional group. The complex was supported on functionalized silica gel to prepare a heterogeneous catalyst (Si-Cu) which was characterized by various analytical techniques. Si-Cu exhibited good catalytic activity in carbon-carbon coupling reactions and showed stability for reuse.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ricardo A. Peralta, Michael T. Huxley, Jorge Albalad, Christopher J. Sumby, Christian J. Doonan
Summary: MOFs offer a unique matrix for isolating and stabilizing specific transition-metal complexes, and an in situ anion metathesis strategy facilitates the post-synthetic modification of Cu(I) complexes appended to MOFs. By exchanging coordinated chloride for weakly coordinating anions in the presence of CO or ethylene, labile MOF-appended Cu(I) complexes featuring CO or ethylene ligands are prepared and structurally characterized. This allows small and moderately sized molecules to access the isolated Cu(I) sites, displacing the place-holder CO ligand, mimicking ligand-exchange processes in Cu-centered catalysis.
INORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Kamila R. Enikeeva, Aliia V. Shamsieva, Anna G. Strelnik, Robert R. Fayzullin, Dmitry V. Zakharychev, Ilya E. Kolesnikov, Irina R. Dayanova, Tatiana P. Gerasimova, Igor D. Strelnik, Elvira I. Musina, Andrey A. Karasik, Oleg G. Sinyashin
Summary: Tertiary diethylpyridylphosphine was synthesized by reaction of pyridylphosphine with bromoethane in suberbasic medium. The reaction of phosphine with copper(I) iodide formed a copper(I) coordination polymer with an intermediate structure containing a copper-halide core. The obtained coordination polymer exhibited green and red emissions, and depolymerization resulted in the formation of a complex with the octahedral structure of the copper-halide core. The coordination polymer can serve as a sensor or detector for overheating processes that need to be maintained at temperatures below 138 degrees C.
Article
Chemistry, Inorganic & Nuclear
Hao Yang, Juan Du, Chun-Li Wang, Shu-Zhong Zhan
Summary: The reaction of en-P-2 with Cu(ClO4)(2) or CuClO4 leads to the formation of two complexes, [Cu-II-en-P-2(NCMe)](ClO4)(2) 1 and [Cu-I-en-P-2]ClO4 2, which exhibit different coordination numbers for the copper atom. The addition of Cu2+ or Cu+ affects the photoluminescence behavior of en-P-2, with a decrease in peak intensities observed at 420 and 560 nm. Furthermore, both copper complexes 1 and 2 show electrocatalytic activity for hydrogen evolution, with complex 1 demonstrating more efficient activity than complex 2.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Franziska Hanusch, Dominik Munz, Joerg Sutter, Karsten Meyer, Shigeyoshi Inoue
Summary: The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene and its consecutive reaction with PPh3AuCl and K2Fe(CO)(4) resulted in the formation of a unique heterobimetallic complex. The complex bears an unusual linear Si-Au-Fe structure with a rare anagostic interaction between the gold atom and a CH bond. Computational analysis shows strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Brandon T. Watson, Anurag Noonikara-Poyil, Adway O. Zacharias, Jana Roithova, H. V. Rasika Dias
Summary: This paper investigates the interactions between copper(I), silver(I), and gold(I) metals and pi-ligands, showing that these interactions are influenced by the electron-donating and electron-withdrawing substituents of the ancillary ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Mukundam Vanga, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: A useful ligand with three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized to stabilize ethylene complexes of copper, silver and gold in coinage metal chemistry.
DALTON TRANSACTIONS
(2022)
Article
Biochemistry & Molecular Biology
Anurag Noonikara-Poyil, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: This study describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support, as well as the details of a related copper(I) complex. Raman data show significant red-shifts in C equivalent to C stretch of different alkynes bound to copper(I), with computational analysis indicating that the interaction is primarily of the electrostatic character. The study also highlights the catalytic activity of a mononuclear copper complex in [3 + 2] cycloadditions and compares its effectiveness with a trinuclear copper catalyst.
Article
Chemistry, Multidisciplinary
Israel Fernandez, Anurag Noonikara-Poyil, H. V. Rasika Dias
Summary: By using relativistic density functional theory calculations, the bonding situation of Ag(I)-CO complexes with a Scorpionate ligand directly attached to the transition metal has been analyzed in detail, showing the main contribution from the electrostatic attractions between the LAg(I) and CO fragments. It has been found that the LAg -> CO pi-backdonation is also significant in these species as well as in related LCu(I)-CO complexes.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Mukundam Vanga, Anurag Noonikara-Poyil, Jiang Wu, H. V. Rasika Dias
Summary: The pyridine-based poly(pyridyl)borates are a recent addition to the scorpionate family, and their applications in the isocyanide and carbonyl chemistry of copper(I) and silver(I) have been described. The X-ray crystal structures of copper and silver complexes reveal that the bis- and tris(pyridyl)borate ligands coordinate to the metal ions using only two pyridyl moieties.
Article
Chemistry, Multidisciplinary
Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: The paper discusses the impact of relativistic effects on the interaction between cationic coinage metal ions and olefins, revealing its influence on bond strength and 13C-NMR patterns. The study finds that the effects of relativity on metal-alkene bonds become more significant as one goes down in the group of elements.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Areli A. Molina-Paredes, Jesus A. Lara-Ceron, Marisol Ibarra-Rodriguez, Casiano del Angel-Mosqueda, H. Rasika Dias, Victor M. Jimenez-Perez, Blanca M. Munoz-Flores
Summary: Nowadays, designing eco-friendly synthesis with high atom economy and low E-factor is one of the biggest challenges for chemists worldwide. Solvent-free reactions are considered one of the best approaches to avoid waste. In this study, a series of solvent-free synthesis of five oxalamides was reported, yielding high purity products. NMR and X-ray diffraction results revealed the characteristic interactions of N,N'-oxalamides.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhou Lu, Mukundam Vanga, Shan Li, Joseph O. O. Adebanjo, Monika R. R. Patterson, H. V. Rasika Dias, Mohammad A. A. Omary
Summary: This study explores the synthesis, structure, and photophysics of a cyclic trinuclear copper(i) complex with iodine substitution, Cu-3[4-I-3,5-(CF3)(2)Pz](3), in comparison with previously reported complexes containing 4-Br/4-Cl groups. The crystal structure is stabilized by various supramolecular interactions, including Cu3MIDLINE HORIZONTAL ELLIPSISI and hydrogen/halogen bonding. Experimental and computational investigations are conducted to study the photophysical properties and supramolecular interactions of all three 4-halo complexes in relation to relativistic effects.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Brandon T. Watson, Mukundam Vanga, Anurag Noonikara-Poyil, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: Bis-and tris-pyridyl borate ligands with pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been synthesized and used in coinage metal chemistry. These ligands allowed for the isolation of group 11 metal-ethylene complexes, with gold complexes showing the largest coordination-induced upfield shifts of the ethylene 13C resonance. Solid-state structures of these complexes revealed the rare K2 coordination mode instead of the typical K3 coordination mode. Computational analyses indicated the favored K2 coordination mode and the strong interaction between gold(I) and ethylene.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mukundam Vanga, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: A unique four-coordinate, classical gold(I)-carbonyl complex with substantial backdonation from gold has been isolated using a special ligand. The study of its lighter analogs of silver(I) and copper(I) enabled the investigation of trends in the coinage-metal family. Computational analysis revealed multiple components in the AuI-CO bonds. The complexes with the special ligand displayed remarkably low C-O stretching frequencies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Mukundam Vanga, Vo Quang Huy Phan, Jiang Wu, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: Thallium(I) complexes of B-methylated and B-phenylated tris(pyridyl)borates with trifluoromethyl groups at the pyridyl ring 6-positions have been synthesized and compared to the tris(pyrazolyl)borate analogues. The coordination modes and spectroscopic features of these complexes have been studied, revealing distinct differences between the two scorpionate families. The steric demands of the ligands have been quantified using the buried volume concept. Ligand transfer chemistry from these complexes to copper(I) under ethylene has also been investigated, and computational analyses of the coordination modes have been performed.
INORGANIC CHEMISTRY
(2023)
Correction
Chemistry, Organic
Panduka B. Koswatta, Rasapalli Sivappa, H. V. Rasika Dias, Carl J. Lovely
Article
Chemistry, Multidisciplinary
Margarita Lopez-Espejel, Marisol Ibarra-Rodriguez, Blanca M. Munoz-Flores, Marcos R. Bahena-Villarreal, Azael A. Cavazos-Jaramillo, Monica D. Garza-Villegas, Cristina Rodriguez-Padilla, Itza E. Luna-Cruz, H. V. Rasika Dias, Juan M. Alcocer-Gonzalez, Victor M. Jimenez-Perez
Summary: The fluorescence imaging technique is widely used in natural and life sciences, but current commercial biomarkers have several disadvantages. In this study, two new fluorescent molecular rotors (SB-B2 and SB-B23) derived from Boron Schiff bases (BOSCHIBAs) were synthesized and characterized. The crystal structure of SB-B23 showed a binuclear complex. Both compounds exhibited viscochromic and thermochromic properties. These low cytotoxicity BOSCHIBAs showed selective fluorescent staining of the endoplasmic reticulum in HeLa cells and HUVECs.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Mukundam Vanga, Benjamin T. Diroll, Alvaro R. Munoz-Castro, H. V. Rasika Dias
Summary: Successful synthesis of sterically demanding diarylboron derivatives and their corresponding copper pyrazolate complexes with modulated photophysical properties is reported in this study. The introduction of secondary diarylboron luminophores and adjustment of the supporting ligand steric features allows for the modulation of the metal pyrazolate's photophysical properties. Computational analysis of the structures and photophysical properties of copper complexes is also presented.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Anurag Noonikara-Poyil, Shawn G. Ridlen, Israel Fernandez, H. V. Rasika Dias
Summary: This report describes the stabilization of Cu(I) and Ag(I) pi-acetylene complexes supported by fluorinated and non-fluorinated, pyrazole-based chelators. These complexes were formed easily in solutions and could be isolated as crystalline solids. Different coordination modes and metal centers were observed, and the coordination shifts of acetylenic carbon resonance were revealed by C-13 NMR spectroscopy. The bonding between the transition metal fragment and the acetylene ligand was found to be stronger in the copper complexes. The C C distance of these complexes was shorter than expected due to incomplete deconvolution of thermal smearing and electron density anisotropy in acetylene.
