Stability and decomposition of gaseous allylcyclopentadienylpalladium

Stauf, Gregory T.; Dowben, Peter A.; Emrich, K.; Barfuss, Steve L.; Hirschwald, W.; Boag, Neil M.

doi:10.1021/j100339a048

Cited by 16 publications

(3 citation statements)

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“…As preliminary characterization, we measured and compared the ionization energies of the three different isomers of closo -dicarbadodecaborane ( ortho -carborane (1,2-C 2 B 10 H 12 ), meta -carborane (1,7-C 2 B 10 H 12 ), para -carborane (1,12-C 2 B 10 H 12 )), and two related icosahedral cage molecules, 1-phospha-2-carbadodecaborane (1,2-PCB 10 H 11 ) and 1-phospha-7-carbadodecaborane (1,7-PCB 10 H 11 ). We determined the adiabatic ionization energy from the first onset of appearance of the parent ion mass peak, similar to previous work. , As illustrated in Figure , the parent ion signal for 1,7-PCB 10 H 11 provides for the adiabatic ionization energy 10.10 ± 0.02 eV. In addition, the vertical ionization energy is derived from a linear extrapolation of the ion signal, as indicated in Figure , yielding 10.22 ± 0.03 eV.…”

Section: Experimental Methodssupporting

confidence: 90%

Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films

et al. 2010

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The dehydrogenation of semiconducting boron carbide (B(10)C(2)H(x)) films as well as the three closo-carborane isomers of dicarbadodecaborane (C(2)B(10)H(12)) and two isomers of the corresponding closo-phosphacarborane (PCB(10)H(11)) all appear to be very similar. Photoionization mass spectrometry studies at near-threshold gas phase photoionization indicate that the preferred pathway for dissociation of the parent cation species (C(2)B(10)H(10)(+) or PCB(10)H(9)(+)) is, in all cases, the loss of H(2). Ab initio density functional theory (DFT) calculations indicate that energetically preferred sites for exopolyhedral hydrogen (B-H) bond dissociation are in all cases at B atoms opposite the C atoms in the parent cage molecule. The site of photodissociation of hydrogen from semiconducting boron carbide (B(10)C(2)H(x)) films, fabricated by plasma-enhanced chemical vapor deposition, is a cage boron atom that can bond to nitrogen upon exposure to VUV light in the presence of NH(3). Shifts in core level binding energies due to nitrogen bond formation indicate that B-N bond formation occurs only at B atoms bound to other boron atoms (B-B sites) and not at B-C sites or at C sites, in agreement with gas phase results.

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Section: Experimental Methodssupporting

confidence: 90%

Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films

et al. 2010

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“…These surface oxygen groups are assumed to be mainly responsible for the dissociative adsorption of the precursor replacing the roughly equally strongly bound allyl and Cp ligands. Obviously, it depends on the reactivity of the surface oxygen groups as to which ligand is dissociated off, because the Pd−Cp and Pd−allyl bond dissociation energies are close . On silica and MCM-41, hydroxyl groups are considered as the anchoring sites of Pd(allyl)(Cp) since only cyclopentadiene was detected during the adsorption. − …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Catalytic Performance of Pd Nanoparticle/Functionalized CNF Composites by a Two-Step Chemical Vapor Deposition of Pd(allyl)(Cp) Precursor

et al. 2009

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Pd nanoparticle/functionalized CNF composites were synthesized by a two-step chemical vapor deposition of Pd(allyl)(Cp) as precursor at atmospheric pressure. Online mass spectrometry was used to measure the gas fragments during the two-step CVD. The functionalized CNFs and the resulting composites were characterized by temperature-programmed desorption mass spectroscopy, inductively coupled plasmaoptical emission spectroscopy, X-ray diffraction, and transmission electron microscopy. The catalytic hydrogenation of cyclooctene on the Pd/CNF nanocomposites was also investigated in a fixed-bed reactor at 40 °C under atmospheric pressure. No palladium deposition was observed on the raw CNFs, as a result of the absence of anchoring sites. The functionalization of CNFs with HNO 3 solution resulted in the formation of surface oxygen groups. The Pd(allyl)(Cp) precursor could be dissociatively adsorbed on the surface of the CNF by the reaction between the ligands and the surface oxygen groups. Further reduction in H 2 formed the Pd/CNF nanocomposites. The palladium loading on the functionalized CNFs depends on the degree of functionalization of the CNFs and on the amount of precursor provided. TEM and XRD results showed that highly dispersed and evenly distributed Pd particles with diameters of 2-4 nm could be prepared by this two-step CVD method. The Pd/CNF nanocomposite catalysts exhibited high activity and stability in the catalytic hydrogenation of cyclooctene, which can be attributed to the special interaction between the palladium nanoparticles and the CNFs and to the mesoporous nature of the CNFs, which prevents mass transfer limitation. The two-step CVD route has great potential in the controlled synthesis of CNF-supported metal catalysts with high dispersion and uniform distribution.

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“…Several studies o f organometallic source compounds, including ( n -a l l y l ) (x-cyclopentadienyl) palladium, suggest t h a t these complexes can be used t o deposit r e l a t i v e l y pure palladium f i l m s [3,4].…”

Section: Introductionmentioning

confidence: 99%

Selective Area Deposition of Conducting Palladium Films on Polyimide Resins

et al. 1989

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W e have demonstrated t h a t the selective area deposition o f palladium on polyimide substrates i s possible through the U.V. photolysis o f ( n -a l l y l ) (n-cyclopentadienyl ) palladium. This p h o t o l y t i c deposition process d i d not r e s u l t i n any apparent damage t o e i t h e r the Ultem 1000 (polyetherimide) o r Kapton substrates (polyimide substrates).The r e s i s t i v i t y o f the palladium f i l m s (< O.lum) suggests t h a t the f i l m s are porous.

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Stability and decomposition of gaseous allylcyclopentadienylpalladium

Cited by 16 publications

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Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films

Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films

Synthesis and Catalytic Performance of Pd Nanoparticle/Functionalized CNF Composites by a Two-Step Chemical Vapor Deposition of Pd(allyl)(Cp) Precursor

Selective Area Deposition of Conducting Palladium Films on Polyimide Resins

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Stability and decomposition of gaseous allylcyclopentadienylpalladium

Cited by 16 publications

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Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B10C2Hx Films

Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B10C2Hx Films

Synthesis and Catalytic Performance of Pd Nanoparticle/Functionalized CNF Composites by a Two-Step Chemical Vapor Deposition of Pd(allyl)(Cp) Precursor

Selective Area Deposition of Conducting Palladium Films on Polyimide Resins

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Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films

Photofragmentation of the closo-Carboranes Part II: VUV Assisted Dehydrogenation in the closo-Carboranes and Semiconducting B₁₀C₂H_x Films