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Journal articles on the topic 'Osmium compounds. Ruthenium compounds. Porphyrins'

Author: Grafiati

Published: 4 June 2021

Last updated: 14 February 2022

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1

Lewis, Jack, and Paul R. Raithby. "Reflections on osmium and ruthenium carbonyl compounds." Journal of Organometallic Chemistry 500, no. 1-2 (September 1995): 227–37. http://dx.doi.org/10.1016/0022-328x(95)00512-o.

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2

Clark, G. R., C. E. F. Rickard, W. R. Roper, D. M. Salter, and L. J. Wright. "Compounds with ruthenium-silicon and osmium-silicon bonds." Pure and Applied Chemistry 62, no. 6 (January 1, 1990): 1039–42. http://dx.doi.org/10.1351/pac199062061039.

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3

Puerta, M. Carmen, and Pedro Valerga. "Ruthenium and osmium vinylidene complexes and some related compounds." Coordination Chemistry Reviews 193-195 (October 1999): 977–1025. http://dx.doi.org/10.1016/s0010-8545(99)00166-6.

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4

LEWIS, J., and P. R. RAITHBY. "ChemInform Abstract: Reflections on Osmium and Ruthenium Carbonyl Compounds." ChemInform 27, no. 8 (August 12, 2010): no. http://dx.doi.org/10.1002/chin.199608303.

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5

Cerón-Camacho, Ricardo, Manuel A. Roque-Ramires, Alexander D. Ryabov, and Ronan Le Lagadec. "Cyclometalated Osmium Compounds and beyond: Synthesis, Properties, Applications." Molecules 26, no. 6 (March 12, 2021): 1563. http://dx.doi.org/10.3390/molecules26061563.

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The synthesis of cyclometalated osmium complexes is usually more complicated than of other transition metals such as Ni, Pd, Pt, Rh, where cyclometalation reactions readily occur via direct activation of C–H bonds. It differs also from their ruthenium analogs. Cyclometalation for osmium usually occurs under more severe conditions, in polar solvents, using specific precursors, stronger acids, or bases. Such requirements expand reaction mechanisms to electrophilic activation, transmetalation, and oxidative addition, often involving C–H bond activations. Osmacycles exhibit specific applications in homogeneous catalysis, photophysics, bioelectrocatalysis and are studied as anticancer agents. This review describes major synthetic pathways to osmacycles and related compounds and discusses their practical applications.

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6

Chen, Hong, Zi-Chao Tang, Rong-Bin Huang, and Lan-Sun Zheng. "Photodissociation Mass Spectrometry of Trinuclear Carbonyl Clusters M3(CO)12 (M = Fe, Ru, Os)." European Journal of Mass Spectrometry 6, no. 1 (February 2000): 19–22. http://dx.doi.org/10.1255/ejms.301.

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Photodissociation of trinuclear carbonyl cluster compounds of Fe, Ru and Os was studied by recording the mass spectra produced from laser ablation of the cluster compounds. Under the experimental conditions, dissociation of the cluster compounds is very extensive, but the dissociation pathway of the osmium cluster is different from those of the iron and ruthenium clusters. The iron and ruthenium clusters not only lost their carbonyl ligands, but their cluster cores were also fragmented. As the osmium cluster dissociated, it ejected three pairs of oxygen atoms, in sequence, before losing the carbonyl ligands, but the trinuclear osmium core did not fragment. This specific dissociation scheme of the osmium cluster reveals its special structural stability. Not only does it have stronger metal-metal bonds, but also a relatively stable coordination bond formed between osmium and carbonyl ligands. In addition, different distributions of positive and negative fragment ions were observed in the experiment. This difference is interpreted as the result of different stabilities of their electronic structures.

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7

Licona, Cynthia, Jean-Baptiste Delhorme, Gilles Riegel, Vania Vidimar, Ricardo Cerón-Camacho, Bastien Boff, Aina Venkatasamy, et al. "Anticancer activity of ruthenium and osmium cyclometalated compounds: identification of ABCB1 and EGFR as resistance mechanisms." Inorganic Chemistry Frontiers 7, no. 3 (2020): 678–88. http://dx.doi.org/10.1039/c9qi01148j.

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8

Walter, Michael G., Alexander B. Rudine, and Carl C. Wamser. "Porphyrins and phthalocyanines in solar photovoltaic cells." Journal of Porphyrins and Phthalocyanines 14, no. 09 (September 2010): 759–92. http://dx.doi.org/10.1142/s1088424610002689.

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This review summarizes recent advances in the use of porphyrins, phthalocyanines, and related compounds as components of solar cells, including organic molecular solar cells, polymer cells, anddye-sensitized solar cells. The recent report of a porphyrin dye that achieves 11% power conversion efficiency in a dye-sensitized solar cell indicates that these classes of compounds can be as efficient as the more commonly used ruthenium bipyridyl derivatives.

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9

Gianino, Jacqueline, and Seth N. Brown. "Highly covalent metal–ligand π bonding in chelated bis- and tris(iminoxolene) complexes of osmium and ruthenium." Dalton Transactions 49, no. 21 (2020): 7015–27. http://dx.doi.org/10.1039/d0dt01287d.

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10

Chambron, Jean-Claude, Jean-Paul Collin, Isabelle Dixon, Valérie Heitz, Xavier J. Salom-Roig, and Jean-Pierre Sauvage. "Synthesis of one-dimensional bis-porphyrinic compounds with a transition metal complex as bridging unit." Journal of Porphyrins and Phthalocyanines 08, no. 01 (January 2004): 82–92. http://dx.doi.org/10.1142/s1088424604000076.

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Linear multicomponent systems, consisting of two porphyrins attached to a central transition metal center, have been prepared and some of their electron- or energy transfer properties have been studied. Each porphyrin is covalently bound to a bidentate or a terdentate ligand, these coordinating molecules being gathered around the metal to afford the desired structure. The spatial arrangement is such that the porphyrinic components are located at both ends of an axis, the transition metal occupying its center. The edge-to-edge distance between the porphyrins is relatively large (~ 20 to 25 Å) and, due to the rigidity of the connectors, it is very well controlled. Three different strategies have been used to construct such assemblies. In the first approach, the porphyrinic fragments are attached at the back of 2,2′,6′,2″-terpyridine ligands (terpy), on the central position (4′). After reaction with an appropriate metal center (ruthenium(II) or iridium(III)), an octahedral complex is obtained which constitutes the central part of the assembly, whereas the porphyrins are at the periphery of the central complex. The second strategy involves the preparation of a 5,5′-disubstituted 2,2′-bipyridine (bipy) ligand followed by its coordination to ruthenium(II). Subsequently, the porphyrinic nuclei are constructed at both ends of the substituents, leading to a linear geometry with a central complex and two laterally-disposed porphyrins. Finally, a very special ligand has been designed and synthesized, which incorporates two 1,10-phenanthroline nuclei (phen). This ligand can wrap itself around an octahedral center (ruthenium(II)) so as to generate a helical arrangement. Both ends of the single-stranded helix can subsequently be attached to porphyrins.

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11

Hanif, Muhammad, Alexey A. Nazarov, Christian G. Hartinger, Wolfgang Kandioller, Michael A. Jakupec, Vladimir B. Arion, Paul J. Dyson, and Bernhard K. Keppler. "Osmium(ii)–versus ruthenium(ii)–arene carbohydrate-based anticancer compounds: similarities and differences." Dalton Transactions 39, no. 31 (2010): 7345. http://dx.doi.org/10.1039/c003085f.

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12

D’Aléo, A., S. Welter, E. Cecchetto, and L. De Cola. "Electronic energy transfer in dinuclear metal complexes containing meta-substituted phenylene units." Pure and Applied Chemistry 77, no. 6 (January 1, 2005): 1035–50. http://dx.doi.org/10.1351/pac200577061035.

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The synthesis and photophysical properties of heterometallic dinuclear complexes based on ruthenium and osmium trisbipyridine units, Ru-mPh3-Os and Ru-mPh5-Os, in which the metal complexes are linked via an oligophenylene bridge centrally connected in the meta position, are described. Electronic energy transfer from the excited ruthenium-based component (donor) to the osmium moiety (acceptor) has been investigated using steady-state and time-resolved spectroscopy. The results obtained for the meta-substituted compounds are compared with the analogous systems in which the phenylene spacers are substituted in the para position. The mechanism of energy transfer is discussed.

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13

Crochet, Pascale, and Victorio Cadierno. "Arene-Osmium(II) Complexes in Homogeneous Catalysis." Inorganics 9, no. 7 (July 12, 2021): 55. http://dx.doi.org/10.3390/inorganics9070055.

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Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. This review article focuses on the catalytic applications of arene-osmium(II) complexes. Among others, transfer hydrogenation, hydrogenation, oxidation, and nitrile hydration reactions, as well as different C-C bond forming processes, are comprehensively discussed.

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14

Gaiddon, Christian, Isabelle Gross, Xiangjun Meng, Marjorie Sidhoum, Georg Mellitzer, Benoit Romain, Jean-Batiste Delhorme, Aïna Venkatasamy, Alain C. Jung, and Michel Pfeffer. "Bypassing the Resistance Mechanisms of the Tumor Ecosystem by Targeting the Endoplasmic Reticulum Stress Pathway Using Ruthenium- and Osmium-Based Organometallic Compounds: An Exciting Long-Term Collaboration with Dr. Michel Pfeffer." Molecules 26, no. 17 (September 4, 2021): 5386. http://dx.doi.org/10.3390/molecules26175386.

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Metal complexes have been used to treat cancer since the discovery of cisplatin and its interaction with DNA in the 1960’s. Facing the resistance mechanisms against platinum salts and their side effects, safer therapeutic approaches have been sought through other metals, including ruthenium. In the early 2000s, Michel Pfeffer and his collaborators started to investigate the biological activity of organo-ruthenium/osmium complexes, demonstrating their ability to interfere with the activity of purified redox enzymes. Then, they discovered that these organo-ruthenium/osmium complexes could act independently of DNA damage and bypass the requirement for the tumor suppressor gene TP53 to induce the endoplasmic reticulum (ER) stress pathway, which is an original cell death pathway. They showed that other types of ruthenium complexes—as well complexes with other metals (osmium, iron, platinum)—can induce this pathway as well. They also demonstrated that ruthenium complexes accumulate in the ER after entering the cell using passive and active mechanisms. These particular physico-chemical properties of the organometallic complexes designed by Dr. Pfeffer contribute to their ability to reduce tumor growth and angiogenesis. Taken together, the pioneering work of Dr. Michel Pfeffer over his career provides us with a legacy that we have yet to fully embrace.

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15

Henke, Helena, Wolfgang Kandioller, Muhammad Hanif, Bernhard K. Keppler, and Christian G. Hartinger. "Organometallic Ruthenium and Osmium Compounds of Pyridin-2- and -4-ones as Potential Anticancer Agents." Chemistry & Biodiversity 9, no. 9 (September 2012): 1718–27. http://dx.doi.org/10.1002/cbdv.201200005.

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16

Beauregard, Paul. "In situ Generation of Ruthenium Tetroxide and Osmium Tetroxide for the Physical Sciences and Their Reaction Indicators." Microscopy Today 10, no. 5 (September 2002): 20–23. http://dx.doi.org/10.1017/s1551929500058314.

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Recently, there was a suggestion on the MSA listserver about the use of osmium tetroxide (OsO4 and how to handle it. One suggestion was that ampoules be scored, placed in a glass jar, and the ampoule smashed to release the contents. This seemed like a very unsafe way to use osmium tetroxide or ruthenium tetroxide. The purpose of this article is to suggest a way to generate smaller amounts of these compounds in a safer manner than smashing ampoules and wondering about what to do with the unused portion after staining or storing. Another purpose is to discuss a new reaction indicator for mainly osmium tetroxide. The use of a reaction specific indicator was mandatory for judging the level or degree to which staining had proceeded in thin sections for the transmission electron microscope (TEM).

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17

Deeming, Antony J., and Andrew M. Senior. "Structural aspects of the osmium and ruthenium clusters [M3(CO)10(alkyne)] and related substituted compounds." Journal of Organometallic Chemistry 439, no. 2 (November 1992): 177–88. http://dx.doi.org/10.1016/0022-328x(92)80228-p.

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18

Laidlaw, William M., and Robert G. Denning. "Synthesis and characterisation of cyanide-bridged heterobinuclear mixed-valence compounds based on cyclopentadienylorganophosphine-ruthenium(II) and -osmium(II) cyano and pentaammine-ruthenium(III) and -osmium(III) moieties." Journal of the Chemical Society, Dalton Transactions, no. 13 (1994): 1987. http://dx.doi.org/10.1039/dt9940001987.

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19

Becalska, Anna, Roland K. Pomeroy, and William A. G. Graham. "Reassignment of the structure of M3(CO)12(Cl)(SnCl3) (M = Ru, Os)." Canadian Journal of Chemistry 67, no. 7 (July 1, 1989): 1236–38. http://dx.doi.org/10.1139/v89-187.

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Reaction of M3(CO)12 (M=Ru, Os) with SnCl4 in benzene at room temperature affords M3(CO)12(Cl)(SnCl3) in essentially quantitative yield. The 13C nmr spectra of these complexes indicate they have a ClM3(SnCl3) arrangement of atoms with the Cl ligand cis and the SnCl3 group trans to a linear Os3 chain. This is contrary to previously proposed structures for these compounds. The 13C nmr spectrum of Os3(CO)12(I)2 which has the iodo ligands cis to the Os3 chain is also reported for comparison. Keywords: ruthenium–tin, osmium–tin, osmium–iodine, l3C nmr spectroscopy.

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20

Bungane, Ntombovuyo, Cathrin Welker, Eric van Steen, and Michael Claeys. "Fischer-Tropsch CO-Hydrogenation on SiO2-supported Osmium Complexes." Zeitschrift für Naturforschung B 63, no. 3 (March 1, 2008): 289–92. http://dx.doi.org/10.1515/znb-2008-0311.

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The conversion of carbon monoxide with hydrogen was studied on a standard Os on SiO2 catalyst at different reaction temperatures, in the range between 200 and 300 °C. Additionally, supported di- and triatomic organometallic Os complexes were tested for their activity in the Fischer-Tropsch synthesis at 220 °C. All compounds showed formation of hydrocarbons, indicating that the organoosmium complexes are indeed active for C─C bond formation. Osmium as Fischer-Tropsch catalyst, however, is approximately 100 times less active compared to ruthenium. Very high methane selectivities (> 90 C-%) were obtained as well as high olefin to paraffin ratios, in particular with the organometallic complexes tested.

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21

Salamakha, P., O. Sologub, J. Stpień-Damm, Yu Prots, and O. Bodak. "Interaction of neodymium and silicon with ruthenium and osmium: phase diagrams and structural chemistry of ternary compounds." Journal of Alloys and Compounds 244, no. 1-2 (November 1996): 161–63. http://dx.doi.org/10.1016/s0925-8388(96)02411-5.

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22

DIXON, ISABELLE M., and JEAN-PAUL COLLIN. "Synthesis and properties of diads based on tetra-aryl porphyrins and ruthenium bis-terpyridine-type complexes." Journal of Porphyrins and Phthalocyanines 05, no. 07 (July 2001): 600–607. http://dx.doi.org/10.1002/jpp.370.

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Four diads consisting of a free-base or zinc aryl-porphyrin associated with two ruthenium(II) bis(terdentate) complexes (non-cyclometallated Ru ( N 6) or cylometallated Ru ( N 5 C )) have been synthesized. The strong electron-withdrawing properties of the Ru ( N 6) as compared to the Ru ( N 5 C ) complex have been illustrated by their electrochemical and spectroscopic properties. Emission spectra of the diads and the reference compounds have shown that very efficient fluorescence quenching occurs, probably by energy transfer processes from the porphyrin to the 3MLCT excited state of the ruthenium unit.

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23

Poddutoori, Prashanth Kumar, Premaladha Poddutoori, and Bhaskar G. Maiya. "Synthesis, spectroscopy and photochemistry of dyads and triads with porphyrins and bis(terpyridine)ruthenium(II) complex." Journal of Porphyrins and Phthalocyanines 10, no. 08 (August 2006): 1049–60. http://dx.doi.org/10.1142/s1088424606000405.

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A bis(terpyridine)ruthenium(II) complex ([Ru]2+) was covalently connected via a floppy - OCH 2 CH 2 O - spacer to the free-base porphyrin (H) or zinc(II) porphyrin (Zn) or both, to obtain dyads ([HRu]2+, [ZnRu]2+) and triads ([HRuH]2+, [ZnRuH]2+, [ZnRuZn]2+). These compounds have been fully characterized by MALDI, UV-vis, 1 H NMR (1D and 1 H -1 H COSY) spectroscopies, and also by the cyclic and differential pulse voltammetric techniques. Absorption spectroscopy of these newly synthesized compounds shows that significant exciton coupling exists in non-polar solvents (cyclohexane and toluene) between the porphyrin ring and the bis(terpyridine)ruthenium(II) complex. Upon excitation within the Soret band of [HRu]2+/[HRuH]2+, free-base porphyrin fluorescence was found to be strongly quenched in non-polar and weakly quenched in polar solvents, probably due to ‘singlet-triplet’ energy transfer from the free-base porphyrin to the [Ru]2+ complex. Whereas, in [ZnRu]2+/[ZnRuZn]2+, zinc(II) porphyrin fluorescence was quantitatively and reasonably quenched in non-polar and polar solvents, respectively by mainly electron transfer from the zinc(II) porphyrin to the [Ru]2+ complex. The solvent plays a crucial role in the photophysical properties of these compounds, since the energy of the triplet metal-to-ligand charge-transfer (3MLCT) excited state is influenced by the polarity of the medium. Finally, [ZnRuH]2+ exhibits the combined fluorescence properties of [HRu]2+ and [ZnRu]2+ but the observed additional quenching in non-polar solvents for the zinc(II) porphyrin component is explained by energy transfer from the zinc(II) porphyrin to the free-base porphyrin and/or the bis(terpyridine)ruthenium(II) complex.

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24

Zykova, A. "Synthesis and Structure of Aryl Phosphorus Compounds." Bulletin of the South Ural State University series "Chemistry" 12, no. 4 (2020): 5–50. http://dx.doi.org/10.14529/chem200401.

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Based on an analysis of the literature published from the late 20th century to the beginning of the 21st century, methods for the synthesis of some complex tetraorganylphosphonium salts are systematized and described, along with the features of the chemical transformations of pentaphenylphosphorus, which was first obtained in 1953. The tetraorganylphosphonium salts were known much earlier, however, the features of the synthesis of transition metal complexes, which are usually obtained from tetraorganylphosphorus halides and metal halides, have not been sufficiently studied. The present review is devoted to the discussion of these topics, since the famous Wittig Reaction is associated with aryl phosphorus compounds, which allows synthesizing alkenes of a given structure, and derivatives of transition metals rightfully occupy a special place among catalysts of various chemical processes. The continuation of these classical studies in the field of chemistry of organoelemental compounds takes place at one of the leading universities in Russia - South Ural State University in the laboratory of chemistry of organoelemental compounds at the Faculty of Chemistry. This article aims at familiarizing the reader with the achievements of Professor V.V. Sharutin and his students in the field of organophosphorus compounds. The main attention is paid to the reactions of pentaphenylphosphorus and its derivatives, as well as methods for the synthesis of ionic complexes of silver, gold, copper, titanium, zirconium, hafnium, ruthenium, osmium, cobalt, rhodium, iridium, palladium and platinum with tetraorganylphosphonium cations. The structural features of the described compounds and the possibility of using transition metal complexes in some catalytic reactions are described.

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25

Halpin, Yvonne, Danilo Dini, Hamid M. Younis Ahmed, Lynda Cassidy, Wesley R. Browne, and Johannes G. Vos. "Excited State Localization and Internuclear Interactions in Asymmetric Ruthenium(II) and Osmium(II) bpy/tpy Based Dinuclear Compounds." Inorganic Chemistry 49, no. 6 (March 15, 2010): 2799–807. http://dx.doi.org/10.1021/ic902140t.

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26

Esteruelas, Miguel A., and Ana M. Lopez. "ChemInform Abstract: Ruthenium- and Osmium-Hydride Compounds Containing Triisopropylphosphine as Precursors for Carbon-Carbon and Carbon-Heteroatom Coupling Reactions." ChemInform 33, no. 33 (May 20, 2010): no. http://dx.doi.org/10.1002/chin.200233275.

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27

Wada, Satoko, Masanobu Shimomura, Tomofumi Kikuchi, Hidetaka Yuge, and T. Ken Miyamoto. "Robust carbene ruthenium-porphyrin catalysts for cyclopropanation reaction of a wide variety of alkenes." Journal of Porphyrins and Phthalocyanines 12, no. 01 (January 2008): 35–48. http://dx.doi.org/10.1142/s1088424608000066.

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A series of carbene ruthenium-porphyrins [ Ru ( por )(: CR 1 R 2)] ( por = TPP ; R 1 = R 2 = p- C 6 H 4 Cl 2, p- C 6 H 4 Me 3, p- C 6 H 4 Ph 4; R 1 = Ph , R 2 = p- C 6 H 4 Ph 6; R 1 = Ph , R 2 = COPh 7; R 1 = p- C 6 H 4 Me , R 2 = CO (p- C 6 H 4 Me ) 8; R 1 = COMe, R 2 = COPh 9; por = TTP ; R 1 = R2 = Ph 1', COPh 5') were synthesized and characterized. The starting material [ Ru ( por )( CO )] was treated with corresponding diazo compounds N 2 CR 1 R 2 in CH 2 Cl 2 or octane for the diaryl carbene complexes 1', 2-4 and 6, while it was subjected to photolysis in THF , followed by reflux with the diazo compounds for the acyl carbene complexes 5' and 7-9. The compounds were robust in octane under reflux and were able to catalyze cyclopropanation reactions with methyl diazoacetate (MDA) toward a wide variety of alkenes. Monocyclopropanation of 25 alkenes was demonstrated with catalyst 3 in octane under reflux. By reaction with more than equimolar amounts of MDA in the presence of catalyst 9, the first porphyrin-catalyzed biscyclopropanation was attained toward nonconjugated α, ω-dienes, viz. 1,5-hexadiene and 1,7-octadiene.

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28

TAKATS, J. "ChemInform Abstract: Synthesis and Chemistry of Dimetallacyclic Compounds: Utility of M(CO) 4(η2-Alkyne) (M: Ruthenium, Osmium) Building Blocks." ChemInform 24, no. 40 (August 20, 2010): no. http://dx.doi.org/10.1002/chin.199340321.

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29

Remita, Hynd, Renée Derai, and Marie-Odile Delcourt. "A new process using radiation for synthesising molecular metal clusters and complexes: First results concerning iron, ruthenium and osmium compounds." International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry 37, no. 2 (January 1991): 221–25. http://dx.doi.org/10.1016/1359-0197(91)90132-l.

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30

Habib, Md Ahsan, Ashish Kumar Sarker, and Masaaki Tabata. "Interactions of DNA with H2TMPyP4+and Ru(II)TMPyP4+: Probable Lead Compounds for African Sleeping Sickness." Bangladesh Pharmaceutical Journal 17, no. 1 (February 21, 2015): 79–85. http://dx.doi.org/10.3329/bpj.v17i1.22321.

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Interactions of DNA with free base porphyrin, tetrakis(1-methylpyridium-4-yl)porphyrin (H2TMPyP4+) and its metallo-derivative of ruthenium(II) have been investigated by UV-Vis, fluorescence and circular dichroism (CD) spectroscopy at 0.1 M NaCl, 7.5 pH and 25 °C. The results suggest that Ru(II)TMPyP4+ interacts with DNA via outside binding in self-stacking manner as indicated by UV-Vis data, a small red shift (?? =3 nm) and a minimal hypochromicity (10%) upon addition of DNA. CD spectra showed the presence of a new peak in the Soret region on addition of Ru(II)TMPyP4+ to DNA solution. On the other hand, the interaction of free base porphyrin, H2TMPyP4+ with DNA revealed a significant hypochromicity (30%) and a large red shift (??=20 nm)in the UV-Vis results which conforms intercalation of free base porphyrin with DNA. In this case, the CD results showed only a negative peak developed in the Soret region during titration with DNA. Fluorescence spectroscopy revealed that initially aggregated porphyrin species were de-aggregated after addition of DNA. This phenomenon has been verified with the fluorescence experiments for the porphyrins in the presence of different concentrations of NaCl and ethanol. Ru(II)TMPyP4+ showed enhanced DNA cleavage in the presence of EcoR1 restriction enzyme, where the enzyme did not cleave DNA. Metallo-porphyrins having the ability to cleave DNA could be used as chemotherapeutic agents for the treatment of African sleeping sickness (Trypanosomiasis). DOI: http://dx.doi.org/10.3329/bpj.v17i1.22321 Bangladesh Pharmaceutical Journal 17(1): 79-85, 2014

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31

Burmakina, G. V., N. I. Pavlenko, and A. I. Rubailo. "The effect of solvents on the stability of the products of electrochemical reactions of iron, ruthenium, and osmium carbonyl cluster compounds." Russian Journal of Inorganic Chemistry 57, no. 8 (August 2012): 1154–57. http://dx.doi.org/10.1134/s0036023612050051.

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32

Stahl, Lothar, Huairang Ma, Richard D. Ernst, Isabella Hyla-Kryspin, Rolf Gleiter, and Manfred L. Ziegler. "Synthetic, structural and PE spectroscopic studies on bis(pentadienyl) compounds of iron, ruthenium and osmium. The role of the heavy metal." Journal of Organometallic Chemistry 326, no. 2 (June 1987): 257–68. http://dx.doi.org/10.1016/0022-328x(87)80161-4.

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33

Leal, Felipe A., Ivan M. Lorkovic, Peter C. Ford, Jonghyuk Lee, Li Chen, Lindsey Torres, Masood A. Khan, and George B. Richter-Addo. "Synthesis, characterization, and molecular structures of nitrosyl nitrito complexes of osmium porphyrins: Disproportionation of nitric oxide in its reaction with Os(P)(CO) (P = porphyrinato dianion)." Canadian Journal of Chemistry 81, no. 7 (July 1, 2003): 872–81. http://dx.doi.org/10.1139/v03-091.

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The Os(P)(NO)(ONO) compounds (P = TTP, TMP, OEP, TmTP; TTP = 5,10,15,20-tetra-p-tolylporphyrinato dianion, TMP = 5,10,15,20-tetramesitylporphyrinato dianion, OEP = octaethylporphyrinato dianion, TmTP = tetra(m-tolyl)porphyrinato dianion) have been prepared from the reaction of the precursor carbonyl complexes Os(P)(CO) with excess nitric oxide. Nitrous oxide was detected as a by-product of the reaction. The IR spectra of the Os(P)(NO)(ONO) compounds (as KBr pellets) reveal bands in the 17901804 cm1 range that are assigned to υNO. The IR spectra also reveal two new bands for each complex in the 14951531 and 913962 cm1 ranges indicative of O-bound nitrito ligands. The linearity of the bound NO groups and the O-binding of the trans nitrito ligands in the Os(P)(NO)(ONO) complexes are evident in the single-crystal X-ray crystal structures of the TTP and TMP derivatives. The kinetics of the reaction were studied by stopped-flow mixing techniques. Spectroscopic analysis of rapidly mixed solutions of Os(P)CO and NO in toluene showed a biphasic approach to the Os(P)(NO)(ONO) and N2O products, owing to the starting material Os(P)CO scavenging CO formed during the reaction to give Os(P)(CO)2 (KCO = 106 M1). The dicarbonyl was the only transient species observed. It is proposed that the rate-determining step of the reaction leading to Os(P)(NO)(ONO) is NO displacement of CO from Os(P)(CO) via initial formation of an unstable 19 electron Os(P)(NO)(CO) intermediate.Key words: osmium, nitric oxide, X-ray, nitrosyl, porphyrin, kinetics.

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Aleksanyan, Diana V., Svetlana G. Churusova, Ekaterina Yu Rybalkina, and Vladimir A. Kozlov. "Rhenium(I) Complexes with Pincer Ligands as a New Class of Potential Antitumor Agents." Proceedings 22, no. 1 (August 8, 2019): 43. http://dx.doi.org/10.3390/proceedings2019022043.

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Transition metal complexes attract continuous research interest as potential antitumor agents. The most popular compounds are ruthenium, gold, titanium, osmium, iridium, zinc, and palladium complexes, which have already displayed cytotoxic features that are not typical for classical platinum-containing chemotherapeutic agents. Substantially lower attention is drawn to organometallic compounds of rhenium. However, the known examples of cytotoxic organometallic rhenium derivatives with bidentate heterocyclic, organophosphorus, labile alkoxide, and hydroxide ligands render further studies in this field very promising. As for their analogs with multidentate ligands, a literature survey has revealed only a few examples of cytotoxic rhenium complexes, whereas the antitumor activity of cyclometallated derivatives has not been studied at all. At the same time, it is known that the use of pincer-type ligands having specific tridentate monoanionic frameworks, which offer multiple options for directed structural modifications, allows one to finely tune the thermodynamic and kinetic stability of the resulting metal complexes. Therefore, we synthesized and studied the cytotoxic properties of a series of rhenium(I) complexes with tridentate pincer-type ligands based on functionalized carboxamides bearing ancillary donor groups both in the acid and amine components. It was shown that the target complexes can be obtained not only by the conventional solution-based method, but also under solvent-free conditions according to the solid-phase methodology recently developed in our group. The results obtained were used to define the main structure–activity relationships for a principally new class of potential antitumor agents and to choose the most promising compounds for further studies in order to create new pharmaceuticals.

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Granozzi, Gaetano, Eugenio Tondello, Renzo Bertoncello, Silvio Aime, and Domenico Osella. "UV photoelectron and theoretical studies of organometal carbonyl clusters of ruthenium and osmium. .mu.-Hydrido-.mu.3-allyl and .mu.-hydrido-.mu.3-allenyl triangulo cluster compounds." Inorganic Chemistry 24, no. 4 (February 1985): 570–75. http://dx.doi.org/10.1021/ic00198a028.

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Sanchez-Delgado, Roberto A., Wonyong Lee, Sung Rack Choi, Yangha Cho, and Moo-Jin Jun. "The chemistry and catalytic properties of ruthenium and osmium complexes. Part 5. Synthesis of new compounds containing arsine ligands and catalytic activity in the homogeneous hydrogenation of aldehydes." Transition Metal Chemistry 16, no. 2 (April 1991): 241–44. http://dx.doi.org/10.1007/bf01032844.

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Arnold, John, Geoffrey Wilkinson, Bilquis Hussain, and Michael B. Hursthouse. "Synthesis and X-ray crystal structure of tetra(2- methylphenyl)molybdenum(IV), Mo(2-MeC6H4)4. Redox chemistry of M(2-MeC6H4)4 compounds of molybdenum, rhenium, ruthenium, and osmium." Journal of the Chemical Society, Dalton Transactions, no. 11 (1989): 2149. http://dx.doi.org/10.1039/dt9890002149.

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Ivon, Ye, V. Le, and Z. Voitenko. "SYNTHESIS OF PHENYLACETYL MIDA BORONATES BY OXIDATIVE CLEAVAGE OF VICINAL DIOLS." Bulletin of Taras Shevchenko National University of Kyiv. Chemistry, no. 1(55) (2018): 50–54. http://dx.doi.org/10.17721/1728-2209.2018.1(55).12.

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A synthetical approach to acyl(N-methyliminodiacetyl)boronates starting from 1-substituted alkenylboronates has been developed. A comparison of different methods of oxidative cleavage of an α-borylated C-C bound was made. It was found, that the best results can be obtained by sequential osmium tetroxide-catalyzed dihydroxylation of an alkene moiety followed by cleavage of the obtained vicinal diol. The cleavage procedure takes place at 0°C in homogeneous conditions (solution of periodic acid in THF) and it is complete in 10 minutes (more prolonged contact with an oxidant solution results in degradation of the target compound). On the other hand, using of ruthenium tetroxide-based reagents results in overoxidation with simultaneous loss of boron moiety. Potassium permanganate protocols leads to the α-borylated-α-hydroxyketone, which is prone to further oxidation. Although 1-alkyl-vinylboronates react smoothly with 3-chloroperbenzoic acid to give corresponding oxiranes (without cleavage of C-B bound), the latter ones are stable toward action of sodium meta-periodate or periodic acid. The results were shown on the model compound – phenylacetyl MIDA boronate. Precursor of this compound, namely, Z-2-(N-methyliminodiacetylboryl)-1-phenylbut-2-ene was prepared in four steps, starting from common-use reagents with 32% overall yield. Thus the new approach allows acetyl MIDA boronates to be prepared just in 6 linear steps. It is remarkable, that mild and homogeneous conditions of the oxidation step permit to carry out this transformation on gram scale. A preliminary investigation of these substances stability towards common methods of working up and purification procedures was made. It was found, that phenylacetyl MIDA boronate and preceding diol, both are stable to storage at ambient conditions (tightly closed vessel, ambient temperature) at least for one month, showing no changes in its NMR spectra. Also, these compounds are stable to extractive work up with NaHCO3, Na2S2O3 and diluted acids. Stability toward chromatography on silica, prolonged contact with water or alcohols is limited. Structures and purity of compounds in this work was established by 1H, 13C – NMR and HPLC-analyses.

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Tooze, Robert P., Geoffrey Wilkinson, Majid Motevalli, and Michael B. Hursthouse. "Alkyl compounds of ruthenium-(III) and -(V) and osmium(III). X-Ray crystal structures of hexakis(trimethylsilylmethyl)- and hexakis(neopentyl)diruthenium(III), dioxohexakis(trimethylsilylmethyl)diruthenium(V), and bis(η3-allyl)tetrakis(neopentyl)diosmium(III)." J. Chem. Soc., Dalton Trans., no. 12 (1986): 2711–20. http://dx.doi.org/10.1039/dt9860002711.

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Clark, George R., Mabel M. P. Ng, Warren R. Roper, and L. James Wright. "Synthesis of monomercurated N-protected pyrroles and the use of these compounds as pyrrolyl group transfer reagents to ruthenium and osmium. Crystal structures of (2-C4H3NC[O]CH3)HgCl, (2-C4H3NC[O]CH3)2 Hg and." Journal of Organometallic Chemistry 491, no. 1-2 (April 1995): 219–29. http://dx.doi.org/10.1016/0022-328x(94)05213-u.

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41

Barkov, Andrei Y., Nadezhda D. Tolstykh, Gennadiy I. Shvedov, and Robert F. Martin. "Ophiolite-related associations of platinum-group minerals at Rudnaya, western Sayans and Miass, southern Urals, Russia." Mineralogical Magazine 82, no. 3 (April 18, 2018): 515–30. http://dx.doi.org/10.1180/mgm.2018.82.

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ABSTRACTWe describe similar assemblages of minerals found in two placers in Russia, both probably derived from an ophiolitic source. The first is located along the River Rudnaya in the western Sayan province, Krasnoyarskiy kray, and the second pertains to the Miass placer zone, Chelyabinsk oblast, in the southern Urals. The platinum-group element (PGE) mineralization in both cases is mostly (at least 80%) represented by alloy minerals in the system Ru–Os–Ir, in the order of occurrence osmium, ruthenium and iridium. The remainder consists of Pt–Fe alloys and species of PGE sulfides, arsenides, sulfarsenides, etc. The associated olivine and amphiboles are supermagnesian, and the chromian spinel has a high Cr# value. The observed enrichment in Ru, typical of an ophiolitic source, may be due to high-temperature hydrothermal equilibration and mobilization in the ophiolite, as is the enrichment in Mg and Cr. Low-temperature replacement of the alloys led to the development of laurite, sulfoarsenides and arsenides. Some placer grains in both suites reveal unusual phases of sulfo-arsenoantimonides of Ir–Rh, e.g. the unnamed species (Rh,Ir)SbS and (Cu,Ni)1+x(Ir,Rh)1–xSb, wherex= 0.2, and rhodian tolovkite, (Ir,Rh)SbS. Two series of natural solid-solutions appear to occur in the tolovkite-type phases. Among the oddities in the Rudnaya suite are globules of micrometric PGE sulfides, crystallites of platinum-group minerals, amphibole, and chalcopyrite bearing skeletal micrometric monosulfide-like compounds (Cu,Pt,Rh)S and (Pd,Cu)S1–x. Pockets of fluxed evolved melt seem to have persisted well below the solidus of the host Pt3Fe-type alloy.

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Sánchez-Delgado, Roberto A., Miriam Medina, Francisco López-Linares, and Alberto Fuentes. "The chemistry and catalytic properties of ruthenium and osmium compounds. Part 7. Regioselective hydrogenation of cinnamaldehyde (3-phenyl-2-propenal) catalyzed by Ru and Os triphenylphosphine complexes in homogeneous solution and by meta-sulfonatophenyl-diphenyldiphosphine (TPPMS) and tris-meta-sulfonato-phenylphosphine (TPPTS) derivatives in an aqueous biphasic system." Journal of Molecular Catalysis A: Chemical 116, no. 1-2 (February 1997): 167–77. http://dx.doi.org/10.1016/s1381-1169(96)00191-4.

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43

Allen, Norman S. "Book Review: Light Harvesting NanoMaterials, Bentham e-Books, ISBN: 978-1-60805-959-1; e-ISBN: 978-1-60805-958-4." Open Materials Science Journal 9, no. 1 (June 26, 2015): 49. http://dx.doi.org/10.2174/1874088x01509010049.

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Light Harvesting NanoMaterials, Bentham e-Books, ISBN: 978-1-60805-959-1;e- ISBN: 978-1-60805-958-4 Edited by Surya Prakash Singh The harvesting, capture and efficient conversion of solar light energy into electrical and heat energy through chemical and structural materials is now a rapid and exciting field of significant advancement and investigation in the scientific world. Many of these novel and often complex materials can attain important developments for many industrial outlets in energy transformation from solar power. This book targets a number of key newly developed nano-materials and consists in total of five chapters each one compiled by authors who are experts in that particular field and is edited by Surya Prakash Singh. The book consists of a number of important topics many developmental in the fields of organic/polymeric nano-materials which brings the reader up-to-date on many important features. The first chapter covers recent investigations covering the inter-locking and embedding of inorganic transistion metal compound based nano-particles onto solar panel surfaces as anti-reflective coatings in order to enhance light absorption characteristics for effective energy conversion. Silicon, titanium and silver compounds in various nano-formats are highlighted. Here the properties of the particles in harvesting light energy as a support and their photochemistry provides many important answers to questions in relation to the efficiencies of energy harnessing. The efficiencies of these processes is examined practically and theoretically in some depth with many very well illustrated devices. Silver nano-particles were particularly valuable and effective in this regard for enhancing solar energy absorption. Nano-crystalline titanium dioxide is a widely investigated material for solar energy harnessing but its inefficiency in absorption like many materials is a major deficiency. In chapter two, the use of doped titanias utilising tetrapyrolic sensitisers and various metal complexes for overcoming this problem is reviewed. Here, the deficiencies of usual ruthenium complexes is superseded via more effective porphyrins, phthalocyanines and corroles and with enhanced coupling i.e. via zinc significant energy conversions may be achieved. The next chapter explores the behavior and properties of polymeric materials as matrices for nano-composites where again energy efficiency conversion is crucial in determining the role of the light induced physic-chemicalprocesses. In this case the design of polymer based nanocomposites is widely assessed and is proving to be one of the most interesting and upcoming fields in solar energy harnessing. Of course, one major setback in this area with organo-materials is durability. In chapter four, one rather interesting area of growing interest in utilising solar energy is that dealing with gold and titania nanoparticles called “plasmonic photocatalysts”. This important field has direct relevance to photo-induced electrical and semiconductor processes aswell as significance in the manufacture of photoelectrochemical catalysts due to their broad visible absorption characteristics and hence high efficiency. In this context, the formulation and properties of the various catalysts can result in the production of novel highly active material complexes with high efficacy for oxidation of organic compounds. In the last chapter C60-based solar cells with copper oxides, CuInS2, phthalocyanines, diamond, porphyrin and exciton-diffusion blocking layers have been fabricated and characterized for use in energy efficient solar cell construction. High efficiencies are observed in all these devices when utilized with C60. To summarize, this important edited text provides the reader with a highly useful and valuable source of scientific information which focuses on many important aspects of development in light energy harvesting processes in both fields of photochemistry and photophysics thus providing many valuable ways forward for further scientific development for the future in solar energy conversion and photocatalysis. It makes interesting reading coupled with many new ideas and is very well illustrated and certainly provides a valuable reference source for chemists, physicists, biologists and engineers working in the field in both academia, government and industry, alike.

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44

García, Hermenegildo. "Preface." Pure and Applied Chemistry 77, no. 6 (January 1, 2005): iv. http://dx.doi.org/10.1351/pac20057706iv.

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Photochemistry is a mature science. A characteristic hallmark of a consolidated scientific discipline is that it increasingly broadens its scope of interests from an initial central core toward the periphery where it interacts with other areas. Most of the current scientific research is characterized by an enriching multidisciplinarity, focusing on topics that combine backgrounds from different fields. In this way, the largest advances are taking place at the interphase between areas where different fields meet.This multidisciplinarity is, I believe, also a characteristic feature of the current situation for photochemistry. Thus, photochemistry was initially focused on the understanding and rationalization at a molecular level of the events occurring after light absorption by simple organic compounds. Molecular organic photochemistry constituted the core of this discipline, and it largely benefited from advances in the understanding of the electronic states provided by quantum mechanics. Later, photochemistry started to grow toward areas such as photobiology, photoinduced electron transfer, supramolecular photochemistry, and photochemistry in heterogeneous media, always expanding its sphere of interest.This context of increasing diversity in topics and specialization is reflected in this issue of Pure and Applied Chemistry. The contributors correspond to some of the plenary plus two invited lectures of the XXth IUPAC Symposium that was held 17ñ22 July in Granada, Spain. The program included plenary and invited lectures and oral contributions grouped in 13 sections covering femtochemistry, photochemistry of biomacromolecules, single-molecule photochemistry, and computational methods in photochemistry to nanotechnology, among others. These workshop titles give an idea of the breadth of themes that were included in this symposium. While it is obvious that the list of contributions correspond to different subdisciplines in photochemistry, all of them have a common scientific framework to rationalize the facts.The purpose of the symposium was to present an overview of the current status of some research fronts in photochemistry. This issue begins with the 2004 Porter Medal Lecture awarded jointly by the Asian, European, and Interamerican Photochemical Societies that was given to Prof. Graham Fleming (University of California, Berkeley) for his continued advances in photosynthesis. Prof. Flemingís studies have constituted a significant contribution to the understanding of the interplay between the structure of photosynthetic centers of green plants and the mechanism of energy migration toward the photosynthetic centers. These events take place in a very short time scale and are governed by the spatial arrangement of the constituents.Continuing with photobiology, the second article by Prof. Jean Cadet (Grenoble University) describes the type of photochemical damage and photoproducts arising from DNA UV irradiation. Knowledge of these processes is important for a better understanding of skin cancer and the possibilities for DNA repair. Closely related with DNA damage occurring upon irradiation, the article by Prof. Tetsuro Majima (Osaka University) provides an account of his excellent work on photosensitized oneelectron oxidation of DNA.The concept of "conical intersection", developed initially by Robb and Bernardi to rationalize the relaxation of excited states, led to the foundation of computational photochemistry, which has proved to be of general application to photochemical reactions. In this issue, Prof. Massimo Olivucci (University of Siena) shows that quantum chemical calculations can also be applied to photochemical reactions occurring in photobiology and, in particular, to the problem of vision. These calculations are characterized by the large number of atoms that are included and the fact that they have to estimate at a high calculation level and with high accuracy the energy of states differring in a few kcal mol-1.The next article corresponds to one of the two invited lectures included in this issue. The one given by Dr. Virginie Lhiaubet-Vallet (Technical University of Valencia) in the workshop Photophysical and Photochemical Approaches in the Control of Toxic and Therapeutic Activity of Drugs describes the enantioselective quenching of chiral drug excited states by biomolecules. Moving from photobiology to free radical polymerization with application in microlithography, the article by Prof. Tito Scaiano (University of Ottawa) reports among other probes an extremely elegant approach to detect the intermediacy of radicals in photochemical reactions based on a silent fluorescent molecular probe containing a free nitroxyl radical.Solar energy storage is a recurrent topic and a long-desired application of photochemistry. In her comprehensive contribution, Prof. Ana Moore (Arizona State University) summarizes the continued seminal contribution of her group to the achievement of an efficient solar energy storage system based on the photochemical generation of long-lived charge-separated states. Another possibility of solar energy storage consists of water splitting. In his article, Prof. Haruo Inoue (Tokyo Metropolitan University) deals with artificial photosynthetic methods based on the use of ruthenium porphyrins as photosensitizers for the two-electron oxidation of water with formation of dioxygen.Also in applied photochemistry, Prof. Luisa De Cola (University of Amsterdam) reports on intramolecular energy transfer in dinuclear metal complexes having a meta-phenylene linker. The systems described by Prof. De Cola have potential application in the field of light-emitting diodes, since most of the complexes described exhibit electroluminescence. The second invited lecture is by Dr. Alberto Credi (University of Bologna), one of Europeís most promising young photochemists. In his interesting article, the operation upon light excitation of a rotaxane molecular machine is described. A macro-ring acting as electron donor moiety in a charge-transfer complex is threaded in a dumbbell-shaped component having two viologen units with different redox potential. Light absorption produces the cyclic movement of the macro-ring from one viologen station to the other.The last two contributions fall within the more classic organic photochemistry realm. Prof. Axel Griesbeck (University of Cologne) describes the multigram synthesis of antimalarial peroxides using singlet-oxygen photosensitizers adsorbed or bonded to polymer matrices. The last contribution comes from Prof. Heinz Roth (University of Rutgers), who has worked during his entire career in the fields of organic photochemistry and radical ion chemistry. Prof. Roth has summarized his vast knowledge in radical ion chemistry, reviewing the mechanism of triplet formation arising from radical ion pair recombination. This mechanism for triplet formation is currently gaining a renewed interest owing to the potential applicability to the development of phosphors.I hope that the present selection will be appealing and attractive for a broad audience of readers interested in photochemistry and will give readers an idea of the state of the art of some current topics in this area.Hermenegildo GarcíaConference Editor

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45

CLARK, G. R., C. E. F. RICKARD, W. R. ROPER, D. M. SALTER, and L. J. WRIGHT. "ChemInform Abstract: Compounds with Ruthenium-Silicon and Osmium-Silicon Bonds." ChemInform 21, no. 47 (November 20, 1990). http://dx.doi.org/10.1002/chin.199047294.

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VENALAINEN, T. "ChemInform Abstract: The Characterization and Catalytic Applications of Heteronuclear Cluster Compounds of Iron, Ruthenium and Osmium." ChemInform 18, no. 40 (October 6, 1987). http://dx.doi.org/10.1002/chin.198740380.

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47

GRANOZZI, G., E. TONDELLO, R. BERTONCELLO, S. AIME, and D. OSELLA. "ChemInform Abstract: UV PHOTOELECTRON AND THEORETICAL STUDIES OF ORGANOMETAL CARBONYL CLUSTERS OF RUTHENIUM AND OSMIUM. μ-HYDRIDO-μ3-ALLYL AND μ-HYDRIDO-μ3-ALLENYL TRIANGULO CLUSTER COMPOUNDS." Chemischer Informationsdienst 16, no. 29 (July 23, 1985). http://dx.doi.org/10.1002/chin.198529074.

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SCHAAL, M., W. WEIGAND, U. NAGEL, and W. BECK. "ChemInform Abstract: PSEUDOHALO METAL COMPOUNDS. LXIV. REACTIONS OF CYANO COMPLEXES OF IRON(II), RUTHENIUM(II), OSMIUM(II), AND PLATINUM(II) WITH α,β-UNSATURATED CARBONYL COMPOUNDS OR KETONES IN THE PRESENCE OF ACIDS: Γ-OXOISOCYANIDE COMPLEXES. X-RAY STRU." Chemischer Informationsdienst 16, no. 40 (October 8, 1985). http://dx.doi.org/10.1002/chin.198540316.

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49

ARNOLD, J., G. WILKINSON, B. HUSSAIN, and M. B. HURSTHOUSE. "ChemInform Abstract: Synthesis and X-Ray Crystal Structure of Tetra(2-methylphenyl)molybdenum(IV), Mo(2-MeC6H4)4. Redox Chemistry of M(2-MeC6H4)4 Compounds of Molybdenum, Rhenium, Ruthenium, and Osmium." ChemInform 21, no. 8 (February 20, 1990). http://dx.doi.org/10.1002/chin.199008253.

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TOOZE, R. P., G. WILKINSON, M. MOTEVALLI, and M. B. HURSTHOUSE. "ChemInform Abstract: Alkyl Compounds of Ruthenium(III) and -(V) and Osmium(III). X-Ray Crystal Structures of Hexakis(trimethylsilylmethyl)- and Hexakis(neopentyl)diruthenium(III), Dioxohexakis(trimethylsilylmethyl)diruthenium(V), and Bis(η3-allyl)tetrakis." ChemInform 18, no. 17 (April 28, 1987). http://dx.doi.org/10.1002/chin.198717303.

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