Reaction of equimolar quantities of MX (M = Au, Cu, X = Cl; M = Ag, X = OTf) and GaCl(3) in CH(2)Cl(2) with P(4) leads to phosphorus ligating a cationic coinage metal centre. For Cu and Ag, ion-contacted coordination polymers are formed; for Au, an ion-separated complex is observed that features the [Au(η(2)-P(4))(2)](+) cation, which is the first homoleptic Au-P(4) complex to be characterised in the condensed phase.
View Article and Find Full Text PDFThe efficient catalytic dehydrocoupling of a range of amine-borane adducts, R'RNH x BH(3) (R' = R = Me 1a; R' = R = (i)Pr 1b; R' = Me, R = CH(2)Ph 1c) by a series of group 4 metallocene type precatalysts has been demonstrated. A reduction in catalytic activity was detected upon descending the group and also on substitution of the cyclopentadienyl (Cp) ligands with sterically bulky or electron-donating substituents. Precatalysts Cp(2)TiCl(2)/2(n)BuLi and Cp(2)Ti(PMe(3))(2), which are believed to act as precursors to [Cp(2)Ti], were found to promote the transformation of 1a to [Me(2)N-BH(2)](2) (3a) in a homogeneous catalytic process.
View Article and Find Full Text PDFFuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes.
View Article and Find Full Text PDFAJR Am J Roentgenol
November 2009
Objective: The purpose of this article is to review the history of permanently implanted brachytherapy sources and to establish methods of identifying radon sources and discussing appropriate management.
Conclusion: There are likely thousands of people bearing radon seeds that continue to emit radiation decades after implantation. They can be identified by clinical history and emission of characteristic x-rays.
We report the development of a facile ring-opening olefin metathesis route to alkaline anion exchange membranes via the copolymerization of a tetraalkylammonium-functionalized norbornene with dicyclopentadiene. The thin films generated are mechanically strong and exhibit high hydroxide conductivities and exceptional methanol tolerance.
View Article and Find Full Text PDFThe Rh(I) complex RhCl(PHCy(2))(3) (1) (Cy = cyclohexyl, C(6)H(11)) has been investigated as a catalyst for the dehydrogenation/dehydrocoupling of dimethylamine-borane adduct Me(2)NH.BH(3) (3) at 20 degrees C to afford the cyclic dimer [Me(2)N-BH(2)](2) (4). Unlike previously studied neutral and cationic Rh(I) precatalysts such as [{Rh(mu-Cl)(1,5-cod)}(2)] and [Rh(1,5-cod)(2)]OTf (1,5-cod = 1,5-cyclooctadiene, C(8)H(12), OTf = OSO(2)CF(3)) with weakly electron-donating ligands at the metal center, which are reduced to catalytically active Rh(0) species, catalytic dehydrogenation of 3 using 1 was found to occur in a homogeneous manner according to nanofiltration experiments, Hg(0) poisoning and kinetic studies.
View Article and Find Full Text PDFThe Fe and Ru phosphine-borane complexes CpM(CO)2PPh2 x BH3 (1, M = Fe, 4, M = Ru) were synthesized utilizing the reaction of the phosphine-borane anion Li[PPh2 x BH3] with the iodo complexes CpM(CO)2I. The Fe complex 1 reacted with PMe3 to yield CpFe(CO)(PMe3)(PPh2 x BH3) (2) and CpFe(PMe3)2(PPh2 x BH3) (3) whereas the Ru species 4 gave only CpRu(CO)(PMe3)(PPh2 x BH3) (5). The complexes 1-5 were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, MS, IR and X-ray crystallography for 1 to 4, and EA for 1, 2 and 4.
View Article and Find Full Text PDFThe compound H3N.BH3 (1) is currently attracting considerable attention as a potential hydrogen storage material. Group 9 catalysts which rapidly and conveniently hydrolyze aqueous 1 in air are described.
View Article and Find Full Text PDFAttempts to induce the catalytic dehydrocoupling of the phosphine-gallane adduct Cy2PH.GaH3 (Cy=cyclohexyl) (1) by treatment with ca. 5 mol% of either the Rh(I) complex [{Rh(mu-Cl)(1,5-cod)}2] (cod=cyclooctadiene) or the Rh(0) species Rh/Al2O3 and [Oct4N]Cl-stabilized colloidal Rh led to catalytic P-Ga bond cleavage to generate the phosphine, H2, and Ga metal.
View Article and Find Full Text PDFThe development of transition-metal-catalyzed dehydrocoupling reactions as a synthetic method for the formation of main-group element-element bonds provides an increasingly attractive and convenient alternative to traditional routes such as salt metathesis/elimination-type reactions. Since the first reported examples in the early 1980s, there has been a rapid expansion of this field, with extensions to a wide variety of metal-mediated homonuclear and heteronuclear bond-forming processes. Applications of this new chemistry in molecular and polymer synthesis, materials science, hydrogen storage and the transfer hydrogenation of organic substrates are attracting growing attention.
View Article and Find Full Text PDFA strained 1-phenyl-2,3-dimethylphosphirene undergoes anionic ring-opening polymerization upon initiation with n-butyl lithium at ambient temperature to yield polyvinylenephosphine, an unsaturated organophosphorus polymer.
View Article and Find Full Text PDFTransition metal catalysis represents a relatively unexplored but potentially useful route to form bonds between main group elements. Previous work in the area of amine-borane adduct dehydrocoupling has exclusively employed late transition metal (e.g.
View Article and Find Full Text PDFThe dehydrocoupling of the fluorinated secondary phosphine-borane adduct R2PH.BH3 (R = p-CF3C6H4) at 60 degrees C is catalyzed by the rhodium complex [{Rh(mu-Cl)(1,5-cod)}2] to give the four-membered chain R2PH-BH2-R2P-BH3. A mixture of the cyclic trimer [R2P-BH2]3 and tetramer [R2P-BH2]4 was obtained from the same reaction at a more elevated temperature of 100 degrees C.
View Article and Find Full Text PDFBorane reagents are widely used as reductants for the generation of colloidal metals. When treated with a variety of heterogeneous catalysts such as colloidal Rh, Rh/Al2O3, and Rh(0) black, BH3.THF (THF = tetrahydrofuran) was found to generate H2 gas with the concomitant formation of a passivating boron layer on the surface of the Rh metal, thereby acting as a poison and rendering the catalyst inactive toward the dehydrocoupling of Me2NH.
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