Article
Chemistry, Inorganic & Nuclear
Kelvin K. H. Tong, Mie Riisom, Euphemia Leung, Muhammad Hanif, Tilo Sohnel, Stephen M. F. Jamieson, Christian G. Hartinger
Summary: In this study, organometallic complexes with a piano-stool structure and di- or tridentate ligand systems were reported, showing improved biological activity and impact on cytotoxic activity.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pablo Rios, Rocio Martin-de la Calle, Pietro Vidossich, Francisco Jose Fernandez-de-Cordova, Agusti Lledos, Salvador Conejero
Summary: A reversible carbon-boron bond formation has been observed in the reaction between a coordinatively unsaturated Pt(ii) complex and tricoordinated boranes, leading to the formation of several intermediate complexes. Computational methods suggest that the kinetic formation of carbon-boron coupling products is under kinetic control, while the platinum boryl species resulting from competitive C-H bond coupling are thermodynamically more stable. These findings provide valuable insights into productive carbon-boron coupling reactions at transition metal centers.
Review
Chemistry, Inorganic & Nuclear
Sourav De, Sabnaz Kazi, Sabyasachi Banerjee, Subhasis Banerjee, Nandan Sarkar, Suraj Kumar Shah, Yung-Chih Kuo, S. K. Ashok Kumar
Summary: This article reviews the literature on the cytotoxic effects and cellular uptake of metal complexes such as ruthenium, iridium, rhodium, and rhenium, with a particular focus on recently developed metal-based complexes. These complexes primarily target DNA and mitochondria, inducing cancer cell apoptosis to reduce adverse drug reactions.
COORDINATION CHEMISTRY REVIEWS
(2024)
Review
Chemistry, Inorganic & Nuclear
Thimma Subramanian Prathima, Badruzzaman Choudhury, Md. Gulzar Ahmad, Kaushik Chanda, M. M. Balamurali
Summary: Numerous biologically active metal complexes have been reported for their unique features and enhanced functions in inhibiting cancer progression. However, many of these drugs have failed at various levels of clinical trials despite performing well in the laboratory.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Li Wei, Rajesh Kushwaha, Anyi Dao, Zhongxian Fan, Samya Banerjee, Huaiyi Huang
Summary: A novel axisymmetric bis-tridentate Ir(iii) photocatalyst (Ir3) with synergetic type I/II photosensitization and photocatalytic activity was reported. Ir3 exhibited high photocytotoxicity against drug-resistant cancer cells under normoxia and hypoxia. The photoactivated anticancer mechanism of Ir3 was investigated in detail. Overall, this new photo-redox catalyst can overcome hypoxia and drug resistance-related problems in clinical anticancer therapy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sara Fernandez-Moyano, Marconi N. Penas-Defrutos, Camino Bartolome, Pablo Espinet
Summary: Analysis of bonding contributions in transition metal complexes [(MCp)-Cp-III*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN-, CNR) revealed a variety of new interactions, including direct lateral donations and hybrid donations, accounting for approximately 20% of the electron donation to the pi*(CO) orbitals.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Alexander J. Bukvic, Arron L. Burnage, Graham J. Tizzard, Antonio J. Martinez-Martinez, Alasdair McKay, Nicholas H. Rees, Bengt E. Tegner, Tobias Kramer, Heather Fish, Mark R. Warren, Simon J. Coles, Stuart A. Macgregor, Andrew S. Weller
Summary: Using solid/gas single-crystal to single-crystal reactivity, a series of sigma-alkane complexes have been prepared and characterized, showing a variety of Rh(I)center dot center dot center dot H-C binding motifs which vary in stability and reactivity based on the size and shape of the alkane. These findings provide insights into guest/host interactions and the role of different environments in metalloenzymes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Ramandeep Kaur, Nidhi Jain
Summary: This review presents recent advances in inter- and intramolecular asymmetric sp(3) C-H bond functionalization utilizing ruthenium, rhodium, and iridium catalysts, and provides insights into the mechanistic aspects of these transformations.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Carley Giffert L. Nongpiur, Charlestine Soh, Danny F. Diengdoh, Akalesh Kumar Verma, Renu Gogoi, Venkanna Banothu, Werner Kaminsky, Mohan Rao Kollipara
Summary: A series of half-sandwich complexes containing 3-acetyl chromen-2one-4(N)-substituted thiosemicarbazone derivatives of ruthenium, iridium, and rhodium were synthesized and evaluated for their antibacterial and anticancer activities. The complexes were characterized using various spectral techniques and X-ray crystallography. The results showed that complex 5 exhibited the highest cytotoxicity in Dalton's lymphoma cells, followed by complex 4, 1, and 2.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Koichiro Masada, Shuhei Kusumoto, Kyoko Nozaki
Summary: In this study, a novel method for synthesizing metallabenzenes by replacing the phosphorus atom in an aromatic phosphinine ring with transition metal fragments was reported. Iridabenzene and rhodabenzene were successfully synthesized by triggering the replacement of the phosphorus atom with iridium and rhodium fragments, respectively. The aromaticity of the newly synthesized metallabenzenes was evaluated experimentally and theoretically.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Chad M. Bernier, Christine M. DuChane, Justin S. Martinez, Joseph O. Falkinham, Joseph S. Merola
Summary: A range of Rh-III and Ir(III) piano-stool complexes were synthesized and characterized, showing high antimicrobial activities against various microbes, particularly Mycobacterium smegmatis. Rh complexes were generally more potent than their Ir analogues, and activity increased with the hydrophobicity of the ligands.
Article
Chemistry, Inorganic & Nuclear
Carley Giffert L. Nongpiur, Danny F. Diengdoh, Nupur Nagar, Krishna Mohan Poluri, Paige M. Gannon, Werner Kaminsky, Mohan Rao Kollipara
Summary: In this study, a series of novel half-sandwich metal complexes were synthesized with different ligands, and the structures were characterized. The antibacterial and antioxidant activities of these compounds were evaluated.
Article
Chemistry, Physical
Jan Patrick Calupitan, Tao Wang, Alejandro Perez Paz, Berta Alvarez, Alejandro Berdonces-Layunta, Paula Angulo-Portugal, Rodrigo Castrillo-Bodero, Frederik Schiller, Diego Pena, Martina Corso, Dolores Perez, Dimas G. de Oteyza
Summary: This paper reports the activation of a C-C sigma bond at room temperature on Cu(111). A biphenylene derivative's C-C sigma bond is broken, followed by the insertion of Cu from the substrate. The study offers new synthetic routes that can be used for in situ generation of activated species for the on-surface synthesis of novel C-based nanostructures. Overall significance of the article is rated 7.5 out of 10.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Fanji Kong, Pablo Rios, Conner Hauck, Francisco Jose Fernandez-de-Cordova, Diane A. Dickie, Laurel G. Habgood, Amor Rodriguez, T. Brent Gunnoe
Summary: We have demonstrated the dimerization and oligomerization reactions of ethylene using bis(phosphino)boryl supported Ni(II) complexes as catalyst precursors. The addition of alkylaluminum(III) compounds or other Lewis acid additives enhances the activity and selectivity of these Ni(II) complexes, leading to the production of butenes and higher olefins. Our studies suggest that this catalysis involves a cooperative activation of ethylene by the Ni-B unit, resulting in the formation of a key borametallacycle intermediate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Li-Jun Zhao, Zequn Yin, Yusheng Shi, Wen Sun, Libo Sun, Huijuan Su, Xun Sun, Weiling Zhang, Linyan Xia, Caixia Qi
Summary: A highly active iridium complex was obtained with an anionic ligand, showing robust cofactor NADH regeneration in physiological conditions. The high activity of the complex can promote enzymatic reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexandra Longcake, Martin R. Lees, Mark S. Senn, Adrian B. Chaplin
Summary: This study describes straightforward procedures for the synthesis of rhodium(I) kappa Cl- chlorocarbon complexes in solution, enabling the isolation of pure products and crystallographic characterization. The results suggest that oxidative addition of C(sp2)-Cl bonds may occur at higher temperatures, while activation of C(sp3)-Cl bonds may proceed through radical mechanisms.
Article
Chemistry, Multidisciplinary
James J. J. Race, Alex Heyam, Matthew A. A. Wiebe, J. Diego-Garcia Hernandez, Charlotte E. E. Ellis, Shixing Lei, Ian Manners, Andrew S. S. Weller
Summary: An amphiphilic block copolymer of polyphos-phinoborane has been synthesized using a mechanism-led strategy and its self-assembly behavior has been studied.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jack Emerson-King, Sudip Pan, Matthew R. R. Gyton, Ralf Tonner-Zech, Adrian B. B. Chaplin
Summary: The synthesis and characterisation of a rhodium(iii) dinitrogen complex, [Rh(2,2 '-biphenyl)(CxP(2))(N-2)](+), are explained in this study. The dinitrogen ligand is positioned inside the cavity of the trans-spanning calix[4]arene-based diphosphine, CxP(2).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ethan W. Poole, Itxaso Bustos, Thomas M. Hood, Jennifer E. Smart, Adrian B. Chaplin
Summary: This article describes the synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand, PONOP-Ar-F, with ortho-trifluoromethylphenyl substituents. The reaction of PONOP-Ar-F with [Ir(biph)(COD)Cl](2) yielded [Ir(PONOP-Ar-F)(biph)Cl], which can be further transformed to [Ir(PONOP-Ar-F)(biph)](+) with an Ir <- F-C bonding interaction. Hydrogenolysis of the biphenyl ligand resulted in the formation of [Ir(PONOP-Ar-F)(H)(2)](+), and subsequent reaction with tert-butylethylene (TBE) allowed the isolation and crystallographic characterization of low valent iridium derivatives.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
M. Arif Sajjad, Stuart A. Macgregor, Andrew S. Weller
Summary: Non-covalent interactions surrounding cationic Rh s-alkane complexes in crystal structures were analyzed using QTAIM and IGMH approaches. Both structures showed the cations residing in an octahedral array of [BAr4F](-) anions, with the [1-NBA](+) cation system exhibiting more C-HF contacts to the anions. QTAIM and IGMH analyses revealed the strongest atom-atom non-covalent interactions between the cation and anion. The IGMH approach highlighted the directionality of C-HF contacts and the significance of C-Hπ interactions.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kramer, F. Mark Chadwick, Stuart A. Macgregor, Andrew S. Weller
Summary: This study uses density functional theory calculations to model the selective exo-H/D exchange in a Rh sigma-alkane complex. The results show that exo-H/D exchange is kinetically more accessible than endo-H/D exchange, and the solid-state environment significantly affects the calculated energetics.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Matthew R. Gyton, Cameron G. Royle, Simon K. Beaumont, Simon B. Duckett, Andrew S. Weller
Summary: The heterogeneous solid-gas reactions of crystals of [Rh(L-2)(propene)][BAr4F] with H-2 and different alkenes and alkynes were investigated using gas-phase NMR spectroscopy. The study provides insights into catalytic pairwise para-H-2 transfer, molecular-level changes in the crystalline catalyst, and the production of high-quality gas-phase spectra. The results reveal the formation of dimeric [Rh(L-2)(H)(mu-H)](2)[BAr4F](2) upon reaction with H-2 and the conversion of NMR silent para-H-2 to NMR active ortho isomer. The hydrogenation of propene and other alkenes and alkynes showed high levels of initial polarization and strong PHIP effects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Anais Coffinet, David Specklin, Quentin Le De, Soukaina Bennaamane, Luna Munoz, Laure Vendier, Eric Clot, Nicolas Mezailles, Antoine Simonneau
Summary: Two different dinitrogen-derived molybdenum nitrido complexes with different geometries, ligand spheres, and oxidation states were found to bond with the strong Lewis acid B(C6F5)(3) through their N ligand. The stable adducts were then used for heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6F5)(2) in a frustrated Lewis pair-type manner. The results showed successful Si-H bond activation and substitution of B(C6F5)(3) by HB(C6F5)(2), depending on the nature of the nitrido complex. No B-H bond splitting was observed. The computed thermodynamics by DFT were consistent with the experimental outcomes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Marc Devillard, Chiara Dinoi, Iker Del Rosal, Clement Orione, Marie Cordier, Gilles Alcaraz
Summary: The palladium-catalyzed annulation reaction of alkynes provides a promising synthetic route to siloles. The mechanism of this reaction has been investigated and it was found that palladasilacyclobutenes formed from the activation of silirenes are key intermediates in the reaction.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kramer, Matthew R. Gyton, Itxaso Bustos, Matthew J. G. Sinclair, Sze-yin Tan, Christopher J. Wedge, Stuart A. Macgregor, Adrian B. Chaplin
Summary: One-electron oxidation of palladium(0) and platinum(0) bis(phosphine) complexes leads to the isolation of a series of linear d(9) metalloradicals [M(PR3)(2)](+) (M = Pd, Pt; R = tBu, Ad), which can remain stable in 1,2-difluorobenzene solution for more than a day at room temperature when combined with the weakly coordinating [BArF(4)](-) counterion. The stability of the metalloradicals decreases in THF, with [Pt(PtBu3)(2)](+) exhibiting the fastest conversion into platinum(II) complexes. The reactions of the metalloradicals with 9,10-dihydroanthracene provide experimental evidence for the C-H bond activation mechanism of platinum. Evaluation: 8 points.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Mathew J. Cross, Claire N. Brodie, Dana G. Crivoi, Joe C. Goodall, David E. Ryan, Antonio J. Martinez-Martinez, Alice Johnson, Andrew S. Weller
Summary: The formation of nanoparticles during the selective production of polyaminoborane [H2BNMeH](n) using [Rh(L1)(η(2):η(2)-H3B center dot NRH2)] [OTf] and [Rh(L1)(NMeH2)][OTf] as catalysts is observed, but there is ambiguity as to whether the catalysis is solely nanoparticle promoted or if there is a molecular homogeneous component.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Akshitha Selvaraj, Marie Cordier, Marc Devillard, Gilles Alcaraz
Summary: A methodological approach for the preparation of unconventional DTE-based photochromic phosphines is reported in this study, and the influence of different linkers on the photochromism and phosphinyl group basicity is studied and evaluated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Joe C. Goodall, M. Arif Sajjad, Emily A. Thompson, Samuel J. Page, Adam M. Kerrigan, Huw T. Jenkins, Jason M. Lynam, Stuart A. Macgregor, Andrew S. Weller
Summary: The group 7 complexes [M(& kappa;(3)-2,6-(R2PO)(2)C5H3N)(CO)(2)L][BAr4F] [M = Mn, R = Pr-i, L = THF; M = Re, R = Bu-t, L = vacant site] undergo solid-gas reactivity with CO in the crystals to form THF substitution products or CO addition products. The [BAr4F] anions show large, local, adaptive changes for M = Mn, while the changes are smaller and remote to the site of reactivity for M = Re.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jack Emerson-King, Adrian B. Chaplin
Summary: The synthesis and solid-state characterization of a heterobimetallic rhodium(III)/silver(I) complex [Rh(2,2'-biphenyl)(CxP(2))Cl]superset of Ag+ is reported, in which CxP(2) is a trans-spanning calix[4]arene-based diphosphine ligand and the silver cation is dative bond to the chloride ligand within the cavity of the macrocycle.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Oliver P. E. Townrow, Andrew S. Weller, Jose M. Goicoechea
Summary: Using Zintl clusters as starting materials, eleven- and twelve-vertex homo- and hetero-multimetallic clusters were synthesized through reactions and stepwise methods. The proposed mechanism based on density functional theory calculations explains the formation of these clusters. These studies provide important insights into the assembly mechanisms of Zintl clusters in solution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)