Supported triosmium clusters, formed from Os3(CO)12 on MgO, were treated in helium at 548 K for 2 h, causing fragmentation of the cluster frame and the formation of mononuclear osmium dicarbonyls. The cluster breakup and the resultant fragmented species were characterized by infrared and X-ray absorption spectroscopies, and the fragmented species were imaged by scanning transmission electron microscopy. The spectra identify the surface osmium complexes as Os(CO)2{Osupport}n (n = 3 or 4) (where the braces denote support surface atoms). The images show site-isolated Os atoms in mononuclear osmium species on MgO. The intensity analysis on the images of the MgO(110) face showed that the Os atoms were located atop Mg columns. This information led to a model of the Os(CO)2 on MgO(110), with the distances approximated as those determined by EXAFS spectroscopy, which are an average over the whole MgO surface; the results imply that these complexes were located at Mg vacancies.
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http://dx.doi.org/10.1021/jz300574u | DOI Listing |
Angew Chem Int Ed Engl
May 2024
Department of Chemistry, Graduate School of Science, Nagoya University, Furo, Chikusa, 464-8602, Nagoya, Japan.
The photocatalytic reduction of carbon dioxide (CO) represents an attractive approach for solar-energy storage and leads to the production of renewable fuels and valuable chemicals. Although some osmium (Os) photosensitizers absorb long wavelengths in the visible-light region, a self-photosensitized, mononuclear Os catalyst for red-light-driven CO reduction has not yet been exploited. Here, we discovered that the introduction of an Os metal to a PNNP-type tetradentate ligand resulted in the absorption of light with longer-wavelength (350-700 nm) and that can be applied to a panchromatic self-photosensitized catalyst for CO reduction to give mainly carbon monoxide (CO) with a total turnover number (TON) of 625 under photoirradiation (λ≥400 nm).
View Article and Find Full Text PDFMaterials (Basel)
December 2021
Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
Recently, mono- and dinuclear complexes have been in the interest of scientists due to their potential application in optoelectronics. Herein, progressive theoretical investigations starting from mononuclear followed by homo- and heterometallic dinuclear osmium and/or ruthenium complexes with NCN-cyclometalating bridging ligands substituted by one or two kinds of heteroaryl groups (pyrazol-1-yl and 4-(2,2-dimethylpropyloxy)pyrid-2-yl) providing the short/long axial symmetry or asymmetry are presented. Step-by-step information about the particular part that built the mixed-metal complexes is crucial to understanding their behavior and checking the necessity of their eventual studies.
View Article and Find Full Text PDFACS Omega
July 2021
Maastricht Science Programme, Faculty of Science and Engineering, Maastricht University, Paul-Henri Spaaklaan, 1, P.O. Box 616, 6200 MD Maastricht, The Netherlands.
Herein, we describe the synthesis, full spectroscopic characterization, DFT (density functional theory) calculations, and single-crystal X-ray diffraction analyses of a series of osmium arene σ-germyl, germanate, σ-stannyl, and stannate complexes, along with their cytotoxic (anticancer) investigations. The known dimer complexes [OsCl(η-CH)] () and [OsCl(η--cymene)] () were reacted with PPh to form the known mononuclear complex [OsCl(η--cymene)(PPh)] () and the new complex [OsCl(η-CH)(PPh)] (); complex was reacted with GeCl·(dioxane) and SnCl to afford, by insertion into the Os-Cl bond, the neutral σ-germyl and stannyl complexes [OsCl(η--cymene)(PPh)(GeCl)] () and [OsCl(η--cymene)(PPh)(SnCl)] (), respectively, as a mixture of enantiomers. Similarly, the reaction of complex with GeCl·(dioxane) afforded [OsCl(η-CH)(PPh)(GeCl)] ().
View Article and Find Full Text PDFiScience
August 2020
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China; Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China. Electronic address:
Mononuclear metal-peroxo species are invoked as the key intermediates in metalloenzymatic or synthetic catalysis. However, either transience or sluggishness reactivity of synthetic analogs of metal-peroxo species impedes our understanding of oxygen activation mechanism. Herein, we designed and characterized a dioxygen-derived mononuclear osmium-peroxo complex, in which the peroxo ligand is stabilized by internally aromatic metallacycle.
View Article and Find Full Text PDFChemistry
September 2020
Department of Chemistry and Biochemistry, University of Hull, Cottingham Road, Hull, HU6 7RX, UK.
Dinuclear metallodrugs offer much potential in the development of novel anticancer chemotherapeutics as a result of the distinct interactions possible with bio-macromolecular targets and the unique biological activity that can result. Herein, we describe the development of isostructural homo-dinuclear Os -Os and hetero-dinuclear Os -Ru organometallic complexes formed from linking the arene ligands of [M(η -arene)(C O )(PTA)] units (M=Os/Ru; PTA=1,3,5-triaza-7-phosphaadamantane). Using these complexes together with the known Ru -Ru analogue, a chromatin-modifying agent, we probed the impact of varying the metal ions on the structure, reactivity and biological activity of these complexes.
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