Showing papers on "Osmium published in 1970"
Patent•
25 Sep 1970
TL;DR: An ELECTRODE for use in an ELECTTOLYTE RESISTANT and ELECTROLYSIS PRODUCT RESISTant MATERIAL is described in this paper, which has a core of a FILM-FORMING METAL and a LAYER having a thickness of about 0.054 micron.
Abstract: AN ELECTRODE FOR USE IN AN ELECTROLYTIC PROCESS. THE ELECTRODE HAS A CORE OF A FILM-FORMING METAL AND A LAYER HAVING AT LEAST THE OUTSIDE PORTION OF THE THICKNESS THEREOF OF AN ELECTTOLYTE RESISTANT AND ELECTROLYSIS PRODUCT RESISTANT MATERIAL, WHICH OUTSIDE PORTION HAS A THICKNESS OF AT LEAST ABOUT 0.054 MICRON. THE LAYER IS ON AT LEAST PART OF THE SURFACE OF SAID CORE. THE MATERIAL OF THE PORTION CONSISTS ESSENTIALLY OF AT LEAST ONE OXIDE WHICH IS AN OXIDE OF AT LEAST ONE PLATINUM METAL TAKEN FROM THE GROUP CONSISTING OF PLATINUM, IRIDIUM, RHODIUM, PALLADIUM, RUTHENIUM, AND OSMIUM. THE ELECTRODE IS ESPECIALLY USEFUL IN ELECTROLYSIS OF BRINE TO OBTAIN CHLORINE.
130 citations
TL;DR: It was found that they react together to form intermediate products which then break down to form osmium black, and glutaraldehyde was revealed as the most effective crosslinking agent by gel filtration and electrophoresis.
Abstract: The reactions between osmium tetroxide and glutaraldehyde and formaldehyde were investigated. It was found that they react together to form intermediate products which then break down to form osmium black. Glutaraldehyde reacts much more rapidly with osmium tetroxide than formaldehyde. The rates of the reactions are increased by increasing the glutaraldehyde concentration or adding bovine serum albumin to the reaction mixture. The reaction rates increase with temperature. The mixtures of fixatives were also tried on tissues and the results paralleled the model experiments. The crosslinking of bovine serum albumin by osmium tetroxide, formaldehyde and glutaraldehyde singly and in mixtures was quantitatively assessed by viscosimetry, gel filtration and disc electrophoresis coupled with densitometry. The crosslinking of bovine serum albumin by pairs of fixatives was less than that produced by the most effective of the pair. After 5 min reaction osmium tetroxide was the most effective crosslinking agent according to viscosimetric experiments, but after one hour's reaction with bovine serum albumin, glutaraldehyde was revealed as the most effective crosslinking agent by gel filtration and electrophoresis.
48 citations
TL;DR: The authors discusses the noble metal catalysts as a group, points out similarities and differences among the metals relevant to the hydrogenation of natural oils, and describes some of the practical applications of catalysis by palladium.
Abstract: Studies in the hydrogenation of natural oils with catalysts of the platinum metals group have been limited mainly to platinum and palladium with only scant attention to rhodium, ruthenium, iridium and osmium. This preference was dictated largely by economics, palladium being the only noble metal catalyst truly competitive on a usecoat basis with nickel in the hydrogenation of low-priced oils. This paper discusses the noble metal catalysts as a group, points out similarities and differences among the metals relevant to the hydrogenation of natural oils, and describes some of the practical applications of catalysis by palladium.
48 citations
Esso1
TL;DR: The specific catalytic activities of the Group VIII noble metals have been determined for the hydrogenation of cyclopropane to propane as discussed by the authors, showing that the metal surface areas required for the determination of specific activities were measured by chemisorption of hydrogen or carbon monoxide at room temperature.
44 citations
TL;DR: In this article, the preparation of M(NO)2L2(M = Ru, Os; L = PPh3) and their oxidation to an oxygen complex Ru(O2)(NO3)(NO)L2, and to hydroxy-dinitrosyl cations, having both linear and bent M-N-O groups is described.
Abstract: The preparation of M(NO)2L2(M = Ru, Os; L = PPh3) and their oxidation to an oxygen complex Ru(O2)(NO3)(NO)L2, and to hydroxy-dinitrosyl cations, [M(OH)(NO)2L2]+, having both linear and bent M–N–O groups is described.
32 citations
TL;DR: In this article, the preparation of cationic hydride complexes of general formula trans-[MH(L)(depe)2] BPh4(M = Fe, Ru, or Os; L = CO, Me3CNC, P(OMe)3, N2, PhCN, etc.; depe = 1,2-bisdiethylphosphinoethane) is reported together with their i.m.r., 1H n.m., and Mossbauer spectra.
Abstract: The preparation of cationic hydride complexes of general formula trans-[MH(L)(depe)2] BPh4(M = Fe, Ru, or Os; L = CO, Me3CNC, P(OMe)3, N2, PhCN, etc.; depe = 1,2-bisdiethylphosphinoethane) is reported together with their i.r., 1H n.m.r., and Mossbauer spectra. A comparison is made between the bonding properties of molecular nitrogen and the other neutral ligands (L) in the series.
32 citations
TL;DR: In this paper, molecular-weight studies on these complexes, both in solution and by mass spectrometry, as well as vibrational spectral work, indicate that they contain three osmium atoms, and this is confirmed by a preliminary X-ray crystallographic study for [Os3(CO)10(AuPPh3)X](X = Cl or Br).
Abstract: Complexes of the general formula [Os3(CO)10(AuPPh3)X](X = Cl, Br, I, or SCN) and [Os3(CO)10(AuPAr3)Cl](Ar = C6H4Me) have been prepared from Os3(CO)12 and [Au(PAr3)X]. Molecular-weight studies on these complexes, both in solution and by mass spectrometry, as well as vibrational spectral work, indicate that they contain three osmium atoms, and this is confirmed by a preliminary X-ray crystallographic study for [Os3(CO)10(AuPPh3)X](X = Cl or Br), which shows each complex to contain a cluster of one gold and three osmium atoms. The thiocyanate complex can be converted into one containing two gold and three osmium atoms. Other products have also been isolated, including [Os3(CO)12–x(PPh3)x], (x = 1–3), and [Os(CO)2(PPh3)2X2](X = Cl, Br, or I). The former are also believed to be trinuclear, whereas the latter are monomers with cis-carbonyl groups and cis-halogen groups. The i.r. and Raman spectra of all the complexes have been recorded in the ranges 2200–1900 and 850–70 cm–1, both in the solid state and where possible also in solution, and assignments for many of the fundamentals are presented.Attempts to prepare analogous silver and copper complexes and ruthenium–gold complexes were unsuccessful.
31 citations
TL;DR: In this article, the preparation and physical properties of binuclear µ-nitrido-complexes of osmium and ruthenium were reported, of the form [M2IVNX8(H2O)2]3]-(M = Os or Ru; X = Cl or Br); [Ru2N(NCS)8(NX)2]-3−; [RuN(NH3)6X3]-2−; RuN(NCS, NCS, or N3);
Abstract: The preparation and physical properties are reported of a number of new binuclear µ-nitrido-complexes of osmium and ruthenium, of the form [M2IVNX8(H2O)2]3–(M = Os or Ru; X = Cl or Br); [Ru2N(NCS)8(H2O)2]3–; [Ru2N(NO2)6(OH)2(H2O)2]3–; [Os2N(NH3)8X2]3+(X = Cl, Br, l, NCS, NO3, or N3); [Ru2N(NH3)8X2]3+(X = Cl, Br, or NO3); [Ru2N(NH3)6X3(H2O)]2+(X = Cl, NCS, or N3). The vibrational spectra suggest that these structures contain linear M–N–M units. Studies of the vibrational spectra of the trimeric species Os3N3(NH3)4(OH)9 and salts containg the [Ir3N(SO4)6(H2O)3]4–,[Ir3N(SO4)6(OH)3]7–, and [Ir3NCl12(H2O)3]4– ions are also reported. The vibrational spectra of mono- and poly-nuclear nitrido-complexes are compared with those of the analogous oxy-systems.
26 citations
TL;DR: In this article, the syntheses of the iron(111), ruthenium(111) and osmium (111) complexes of dithioacetylacetone are described.
Abstract: The syntheses of the iron(111), ruthenium(111), and osmium(111) complexes of dithioacetylacetone are described. The tris chelates are neutral low-spin (S = 1/2)monomers. Polarography in acetone reveals a ready one-electron reduction for each complex. Infrared and e.s.r. spectra are reported. The magnetic susceptibilities have been measured as a function of temperature. The electronic absorption spectra are compared with those of the related cobalt(111) group complexes, and some tentative assignments of charge transfer bands are provided.
25 citations
21 citations
TL;DR: In this article, a mechanism is proposed to account for the various products of the reactions between Group IVB hydrides R3MH and the dodecacarbonyls of the iron triad.
Abstract: Trimethyl-and triethyl-silane react with dodecacarbonyltriosmium at elevated temperatures or under u.v. irradiation in hexane to form the complexes R3SiOs(CO)4H, (R3Si)2Os(CO)4, and [R3SiOs(CO)4]2(R = Me or Et). These compounds are inter-related both thermally and upon further reaction with R3SiH. From the reaction between Me3SnH and Os3(CO)12 only Me3SnOs(CO)4H and (Me3Sn)2Os(CO)4 are isolated. Treatment of [Me3SiOs(CO)4]2 with sodium amalgam affords [Me3SiOs(CO)4]–, from which the species Me3SiOs(CO)4X (X = H, Me, SnMe3, or Ru(CO)4SiMe3) have been obtained. The n.m.r., i.r., and mass spectra of the new compounds are reported. A mechanism is proposed to account for the various products of the reactions between Group IVB hydrides R3MH and the dodecacarbonyls of the iron triad.
TL;DR: In this paper, a reduction of osmium(VIII) by ascorbic acid has been studied in the presence of hydrochloric acid, and the reaction is found to be directly proportional to the concentration of OSA and HOI and to the reciprocal of the hydrogen ion concentration.
Abstract: Reduction of osmium(VIII) by ascorbic acid has been studied in the presence of hydrochloric acid. The reaction is found to be directly proportional to the concentration of ascorbic acid and osmium(VIII) and to the reciprocal of the hydrogen ion concentration. In the proposed mechanism, the reacting species have been shown to be perperosmic acid and ascorbate ion; this was supported by the negligible effect of the ionic strength. Influence of temperature was studied in the range 25–40 °C, and the energy and entropy of activation were calculated as 14.1 ± 0.2 kcal mole−1 and −8.6 ± 0.1 e.u., respectively. Osmium(IV) was found to be a product of the reaction.
TL;DR: In this paper, the lowest energy charge transfer bands in the spectra of some phosphine and arsine complexes of rhenium, ruthenium and iridium were assigned and their energies rationalised by the concept of optical electronegativity.
Abstract: The charge-transfer bands in the spectra of some phosphine and arsine complexes of rhenium, ruthenium, osmium, iridium, and platinum are described. The lowest-energy charge-transfer bands have been assigned and their energies rationalised by the concept of optical electronegativity.
TL;DR: In this paper, the formation of a 1 : 1 complex of osmium(v111) and the anion of the organic acid followed by decomposition to intermediate products with hydroxide ion was investigated.
Abstract: The alkaline ferricyanide oxidations of tartrate and malate ions have been studied in the presence of osmium tetroxide used as catalyst. The rates are consistent with a mechanism involving as the first step the formation of a 1 : 1 complex of osmium(v111) and the anion of the organic acid followed by decomposition to intermediate products and the osmium(v1) species with hydroxide ion. The osmium(V1) thus produced is rapidly oxidized to osmium(V111) with ferricyanide. The kinetic data obtained at higher tartrate concentrations indicate the formation of an osmium(v111)-(tartrate)2 complex that is resistant to decomposition. The possibility of the formation of osmium(V1)-organic anion complexes, causing a retarding effect on the reaction velocity during a kinetic run, is also discussed. The oxidation products are determined and a possible set of reactions for their formation is set out.
TL;DR: Osmium nitrosyl derivatives, of formula OsX3(NO)L2 [X = Cl, Br, I; L = P(C6H5)3, As(C 6H5), Sb(Sb)3], are reported in this paper, in which the structure of these new compounds are discussed on the basis of their i.r. and electronic spectra.
TL;DR: A series of 12 dinitrogen complexes of osmium(II), mer-[OsX2(N2)(QR3)3]-X = Cl or Br; QR3= tertiary phosphine or arsine has been prepared by the zinc reduction under dinitrogens of solutions of mer[OsX3(QR 3] in anhydrous tetrahydrofuran (THF) as discussed by the authors.
Abstract: A series of 12 dinitrogen complexes of osmium(II), mer-[OsX2(N2)(QR3)3](X = Cl or Br; QR3= tertiary phosphine or arsine) has been prepared by the zinc reduction under dinitrogen of solutions of mer-[OsX3(QR3)3] in anhydrous tetrahydrofuran (THF). The compounds are assigned the meridional configuration with dinitrogen trans to halogen on the basis of their n.m.r. and i.r. spectra. The co-ordinated dinitrogen is displaced quantitatively by diphosphine Ph2P·CH2·CH2·PPh2 or by halide ion in the presence of air. Attempts to prepare an analogous series of complexes of ruthenium(II) were unsuccessful.
Patent•
17 Sep 1970TL;DR: In this paper, a process for the conversion of olefinic hydrocarbons according to the ODE reaction (e.g., the ole fin disproportionation reaction) by contacting the oleinic hydrocarbon with a catalyst comprising a compound of ruthenium, iron, osmium, rhodium, cobalt or iridium complexed with a selected complexing agent was described.
Abstract: A process for the conversion of olefinic hydrocarbons according to the olefin reaction (e.g., the olefin disproportionation reaction) by contacting the olefinic hydrocarbon with a catalyst comprising a compound of ruthenium, iron, osmium, rhodium, cobalt or iridium complexed with a selected complexing agent (e.g., triphenylphosphine) and combined with an organoaluminum compound (e.g., methylaluminum sesquihalide). A process of preparing rhodium and iridium NO-containing complexes is described. Metal complexes which contain both NO and NO2 complexing agents are also described.
TL;DR: In this paper, it was shown that pyrolysis of the compounds (Me3Ge)2M′(CO)4[M′= Ru or Os] affords polynuclear complexes [Me2GeM′ (CO)3]3 shown to contain heterocyclic rings of six metal atoms.
Abstract: Pyrolysis of the compounds (Me3Ge)2M′(CO)4[M′= Ru or Os] affords polynuclear complexes [Me2GeM′(CO)3]3 shown to contain heterocyclic rings of six metal atoms, and the anion [Me3GeRu(CO)4]– reacts with various metal halides to give inter alia pentanuclear [Me3GeRu(CO)4]2Hg.
TL;DR: The crystal structure of Os4O4(CO)12 has been determined by X-ray diffraction and found to contain four equivalent osmium atoms arranged in the form of a cube with Os(O)3 groups alternating with O atoms at the corners as discussed by the authors.
Abstract: The crystal structure of Os4O4(CO)12 has been determined by X-ray diffraction and found to contain four equivalent osmium atoms arranged in the form of a cube with Os(CO)3 groups alternating with O atoms at the corners.
TL;DR: The reaction of [ReCl(N2)(Ph2PCH 2·CH2·PPh2)2] with silver salts, cupric chloride, ferric chloride or halogens produces salts of the anion [Recl(N 2 )+]+, and there is no suggestion of any bridged species as discussed by the authors.
Abstract: The reaction of [ReCl(N2)(Ph2PCH2·CH2·PPh2)2] with silver salts, cupric chloride, ferric chloride, or halogens produces salts of the anion [ReCl(N2)(Ph2PCH2·CH2·PPh2)2]+, and there is no suggestion of any bridged species.
TL;DR: The osmium-mercury compound, OsCl2(HgCl)(NO)(PPh3)2, was formed by oxidative addition of HgCl2 to OsCl(CO)(NO)2 as mentioned in this paper.
Abstract: The osmium–mercury compound, OsCl2(HgCl)(NO)(PPh3)2 is formed by oxidative addition of HgCl2 to OsCl(CO)(NO)(PPh3)2; its crystal structure reveals octahedral co-ordination about osmium with an Os–Hg distance of 2·577 A and a linear Os–N–O linkage.
TL;DR: In this article, the β-decay, 187 Re → 187 Os, has a sufficiently long half-life to have applications in geology for both dating and natural isotopic tracer studies and improvements in analytical techniques are urgently needed to explore these applications and to establish the detailed geochemical relationships of rhenium and osmium with greater certainty.
01 Jan 1970
TL;DR: Halogens, mercury, lithium and osmium concentration measurements in Apollo 11 samples, using neutron and photon activation as mentioned in this paper, were performed using the Apollo 11 Apollo 11 data set.
Abstract: Halogens, mercury, lithium and osmium concentration measurements in Apollo 11 samples, using neutron and photon activation
TL;DR: In this article, aqueous solution of known dinitrogen complexes was shown to produce transient [Os(NH3)5N2]3+ and [(NH3]5RuN2Ru(NH 3)5]5+ ] species with decomposition rate constants of 0·02 sec-1 and 0·10 sec−1, respectively.
Abstract: Electrochemical oxidation of known dinitrogen complexes in aqueous solution has been shown to produce transient [Os(NH3)5N2]3+ and [(NH3)5RuN2Ru(NH3)5]5+ species with decomposition rate constants of 0·02 sec–1 and 0·10 sec–1, respectively; no [Ru(NH3)5N2]3+ was detected.
TL;DR: In this paper, two methods for the fabrication of self-supporting isotopically enriched targets of osmium suitable for use in nuclear reaction and scattering experiments are described, one leading to thin targets of 2, the other to targets of many mg/cm 2.