Formation of methyl platinum complex in the reaction of methane with chloroplatinic acid

The¹HNMR method and chemical analysis indicate that a complex of Pt(IV) containing a CH₃–Pt fragment is formed in the reaction of H₂PtCl₆+H₂PtCl₄ with methane at 120 °C in aqueous CF₃CO₂H. The complex was isolated from the solution as an adduct of Ph₃P.

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, H₂PtCl₆ H₂PtCl₄ CF₃COOH 120°C (IV), Pt–CH₃. Ph₃P , .

     

Pyrolysis of chloroplatinic acid to directly immobilize platinum nanoparticles onto multi-walled carbon nanotubes

Platinum nanoparticles supported on multi-walled carbon nanotubes (Pt/MWCNTs) were first prepared by simple pyrolysis of H₂PtCl₆ solution. The structure of Pt/MWCNTs was characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), and the results showed that the diameter of the obtained platinum nanoparticles immobilized on MWCNTs was below 50 nm, although the obtained platinum nanoparticles were not well uniformly dispersed on the surface of MWCNTs. The electrocatalytic performance of Pt/MWCNTs electrode for methanol oxidation reaction (MOR) was also investigated by linear sweep voltammetry (LSV), indicating that it was possible to employ the obtained platinum nanoparticles as anode material in fuel cell. Developing a novel and simple method to prepare platinum nanoparticles onto MWCNTs is the main contribution of this letter. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 8, pp. 1050–1053. The text was submitted the authors in English.     

Use of a heterogeneous isotope exchange method for preparation of rose bengal labelled by radioisotopes of iodine

A new method of preparation of rose bengal labelled by radioisotopes of iodine has been developed. The method is based on heterogeneous isotope exchange between rose bengal absorbed on a solid carrier and electrophilic species of radioiodine in HCl solutions. Low specific activity solutions can be used in the method. The method can also be used for preparation of other labelled derivatives of diiodofluorescein.     

Studies on some organic platinum complexes labelled with169Yb

The reaction of platinum-methionines and platinum-selenomethionine complexes with ytterbium chloride was studied. The biodistribution of these organic platinum complexes labelled with¹⁶⁹Yb was examined in animals bearing Ehrlich tumor. It was found that the retention of radioactivity from labelled monomethionin- and monoselenomethioninplatinum complexes in animals after 72 h was about 60% while the retention from dimethioninplatinum complex was about 6%.     

The preparation of astatine labelled tyrosine using an electrophilic reaction

Carrier-free astatotyrosine has been synthesized using an electrophilic reaction in acidic media. Temperature of 150–160°C and reaction time of 20–30 min were chosen as optimal conditions for the synthesis of astatotyrosine. Under the selected conditions the yield was about 90%.     

The preparation and characterization of a platinum ether complex

The reaction of [Pt((F₃C)CCH(CF₃))(P(C₂H₅)₃)₂CH₃OH]PF₆ with allene in methanol affords a novel metallocyclic ethereal complex [$\text{Pt((F}{}_3\text{C)CHC(CF}{}_3\text{)C(CH}{}_3\text{)CH}{}_2\text{O}$CH₃)(P(C₂H₅)₃)₂]PF₆, which has been characterized by ¹H, ²H, ¹⁹F and ³¹P NMR spectroscopy. Its structure has also been determined by a single crystal X-ray analysis. The crystal are monoclinic, space group P2₁/n, with cell dimensions a 20.012(5), b 17.222(5), c 8.902(3) Å and β 91.54(5)°. The structure was refined by full matrix least-squares methods on F, using 3097 unique observations collected by automated four circle diffractometer. Refinement converged at R  0.066. The Pt atom has a distorted square-planar coordination geometry, with cis P atoms, and PtP distances of 2.219(4) Å (trans to O) and 2.324(4) Å (trans to C). These results show the ethereal group is a weak ligand to platinum(II) but because of the chelating effect, its displacement by other ligands is thermodynamically not favorable. The mechanism of formation of the ethereal complex is also discussed.     

Synthesis of labelled dihydroartemisinic acid

[15-¹³C²H₃]-Dihydroartemisinic acid (2a), [15-C²H₃]-dihydroartemisinic acid (2b) and [15-¹³CH₃]-dihydroartemisinic acid (2c) have been obtained in good yield and high isotopic enrichment by a reconstructive synthesis from artemisinin. These labelled compounds were designed to be used in biosynthetic experiments to determine the origins of artemisinin and other sesquiterpene natural products from Artemisia annua.     

Reactions of methylated cyclopropanes and olefins with chloroplatinic acid. I. Diacylation and pyrylium ion formation

In contrast to cyclopropane itself, simple methyl-substituted cyclopropanes do not produce platinum insertion products upon reaction with chloroplatinic acid in acetic anhydride. Instead, the major products are aromatic heterocyclic cations, the pyrylium ions, which are formed as the result of diacylation of the cyclopropane ring and subsequent dehydration and ring closure to the aromatic heterocycle. Similar products are formed from the diacylation of certain olefins in the presence of chloroplatinic acid in anhydride solvents. The combination of solvent and substrate variations has led to a proposed mechanism for these reactions which demonstrates the essential and unique mole of platinum. In particular, the specific pyrylium ions produced are formed as a consequence of initial activation of the least-substituted cyclopropane ring bond by insertion of platinum, followed by acylation of platinum-bonded carbon, proton loss to a β,γ-unsaturated carbonyl, a second acylation, and, finally, ring closure.     

Reactions of methylated cyclopropanes and olefins with chloroplatinic acid II. Monoacylation and the formation of β,γ-unsaturated carbonyl complexes of platinum dichloride

Upon reaction with chloroplatinic acid in acid anhydride solvents, several methyl-substituted cyclopropanes and olefins form platinum dichloride adducts of β,γ-unsaturated carbonyls in which the ligand is bound to platinum through both the olefin π-system and a lone pair on the carbonyl oxygen. The cyclopropane reactions are shown to proceed initial isomerization to an olefin, followed by acylation and proton loss. The stereochemistry of the products is shown to be dependent upon the substitution on the carbons α and β to the carbonyl, and in the case where both the α- and β-carbons are methyl-substituted a single conformation cf the product is isolated.     

The platinum benzole acid blues — a new class of blue platinum compounds

Summary The preparation of platinum blues from Pt(NH₃)₂(H₂O) ₂ ²⁺ and benzoic or phthalic acids is described. The compounds were characterised by e.p.r., u.v./vis. and x-ray photoelectron spectroscopy. Unlike pyrimidine blues, the platinum blues reported here appear to be non-ionic.     

Surfactant-free preparation of supported cubic platinum nanoparticles

A novel method has been developed for preparing supported cubic platinum nanoparticles. Carbon monoxide and hydrogen are used to reduce platinum precursors present at a solid-gas interface and to control the shape of the growing Pt nanoparticles. By avoiding the use of any organic agents in the synthesis, cubic Pt particles free of hydrocarbons are formed, thereby avoiding possible contamination of the catalyst surface. The approach used is simple and readily scalable.     

The preparation and cytotoxic properties of211at labelled concanavalin a bound to cell membranes

A method of labelling biologically active proteins with the alpha emmitting halogen²¹¹At is presented. The labelling procedure is discussed with reference to the chemistry of astatine. Proteins which have been labelled retain approximately 50% of their original biological activity. Using cell specific labelled proteins, dose response curves are given indicating that such reagents are extremely cytotoxic, D₃₇ human CML cells=5 atmos²¹¹At/cell. The research potential of²¹¹At labelled biologically active proteins is briefly discussed.     

Isotopic ion exchange separation of radioisotopes using an acetone-water-hydrochloric acid system

Isotopic ion exchange for the rapid separation of radioactive mixtures has been further extended through the use of an acetone-water-hydrochloric acid system. Distribution data were obtained for 27 elements in the range of 15–90% acetone, 0.3N HCl indicating a number of new separations. The approach was used for the separation of several radioisotopes from short half-life magnesium matrix for activation analysis. The separations were completed in less than 5 minutes. Research supported by the Advanced Research Projects Agency.     

Electrochemical preparation of platinum nanothorn assemblies with high surface enhanced Raman scattering activity

Platinum nanothorn assemblies with sharp tips and edges were prepared, which exhibit high surface enhanced Raman scattering (SERS) activity and yield an enhancement factor as high as 2000 for adsorbed pyridine.