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Role of High-Spin Species and Pendant Amines in Electrocatalytic Alcohol Oxidation by a Nickel Phosphine Complex
We report the development of active and efficient electrocatalysts for oxidation of alcohols using earth-abundant metals will aid the progress towards a renewable energy economy. Here we present a detailed mechanistic study of electrocatalytic benzyl alcohol oxidation by a molecular nickel complex containing pendant amines using a combination of kinetic studies, NMR spectroscopy, and density functional theory. The catalyst preferentially binds alcohol in high-spin octahedral geometry, but this complex is not readily deprotonated by exogeneous base and inhibits catalysis. Dissociation of one or more solvent ligands returns the complex to a low-spin state that can be deprotonated. Kinetic modeling indicates the off-cycle high-spin intermediate lowers the catalytic turnover frequency by a factor of eight, suggesting that substantial gains in activity can be attained by improvements to the catalyst coordination geometry. In a second finding, we demonstrate the pendant amine of the catalyst only functions as a proton relay for the potential-determining step, oxidation of a nickel hydride intermediate, but does not have a substantial impact on the overall rate for oxidation of benzyl alcohol to benzaldehyde. This result contradicts the common expectation for pendant amines to participate in rate-limiting proton transfer reactions.
ESI-MS Identification of the Cationic Phosphine-Ligated Gold Clusters Au1-Au22: Insight into the Gold-Ligand Ratio and Abundance of Larger Clusters
Triphenylphosphine (PPh3)-ligated gold clusters offer promising potential applications due to their relative ease of synthesis and usefulness in forming advanced cluster architectures. While previous studies reported cationic PPh3-ligated gold clusters with core sizes of Au1 - Au4, Au6 - Au11, and Au¬13 - Au14, there has not been definitive identification by mass spectrometry of larger clusters in the Au12 - Au25¬ range. Herein, we survey a polydisperse solution of cationic PPh3-ligated gold clusters using high mass-resolution (M/?M = 60,000) electrospray ionization mass spectrometry (ESI-MS). To improve the sensitivity and mass resolution of larger clusters for unambiguous identification, we increased the number of scan averages and reduced the range of mass collection windows to 200 m/z, thereby mitigating potential mass and ion abundance bias resulting from smaller “building block” gold clusters and other solution components present in higher abundance. In addition to the previously reported clusters, we identified several new species including Au5(PPh3)5+, Au12(PPh3)9HCl2+, Au15(PPh3)9Cl2+, Au16(PPh3)10Cl22+, Au17(PPh3)113+, Au18(PPh3)102+, Au19(PPh3)10Cl2+, Au20(PPh3)12H33+, Au21(PPh3)10Cl2+, and Au22(PPh3)10Cl22+, indicating that a full range of clusters between Au1 - Au22 may be observed in a single polydisperse solution. Considering all of the observed clusters, our findings provide evidence that the “magic number” icosahedral Au13 may be the transition point in cluster growth between smaller clusters, exhibiting a 1:1 gold-to-ligand ratio, and larger clusters, wherein subsequent gold atoms are added to the core without an equal number of accompanying ligands. Our method demonstrates that reducing the range of m/z collection windows and increasing the number of scan averages can improve instrument sensitivity for cationic gold clusters and enable a more complete survey of polydisperse solutions, thereby providing new insights to guide and validate the results of other characterization methods and theoretical calculations. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MH acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. HH acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). This work was performed using EMSL, a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle.
Improving the theoretical description of Ln( iii )/An( iii ) separation with phosphinic acid ligands: a benchmarking study of structure and selectivity
Density functionals with high exact exchange ( E HFX ≥ 50%) show the best agreement with CCSD(T)-DKH2 Am( iii )/Eu( iii ) selectivities and MP2-DKH2 distances.
Synthesis, characterization, and theoretical analysis of a plutonyl phosphine oxide complex
The interplay of bond strength and covalency are examined in AnO 2 Cl 2 (OPcy 3 ) 2 (An = Pu, U) complexes. The synthesis of trans-PuO 2 Cl 2 (OPcy 3 ) 2 , 1-Pu, has been carried out and confirmed by single crystal X-ray diffraction along with UV-vis-NIR, and 31 P NMR spectroscopies. Theoretical analysis finds that despite a higher calculated covalency for the Pu–Cl interaction, the Pu–OPcy 3 interaction is stronger due to the accumulation of electron density in the interatomic region. As a result, the coordination of equatorial ligands slightly decreases the strength of the Pu≡O yl interactions relative to the free gas phase (PuO 2 ) 2+ ion.
The preparation and properties of vapor- deposited epitaxial InAs sub 1-x P sub x using arsine and phosphine.
Vapor phase epitaxial production of indium arsenic phosphide crystalline layers, discussing electron mobilities, electrical resistivities and doping
The delta and pi effects of phosphines, pyridines, and amines in LW/CO/5 complexes
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Absolute rate constant for the reaction of atomic hydrogen with phosphine over the temperature range 209 to 495 K
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Phosphine in Jupiter's atmosphere - The evidence from high-altitude observations at 5 micrometers
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The middle-infrared spectrum of Saturn - Evidence for phosphine and upper limits to other trace atmospheric constituents
Observations of Saturn at high spectral resolution in the middle-IR spectral region (2.5-5.6 microns) were obtained using a Fourier spectrometer at ground-based and airborne observatories. These spectra establish that PH3 exists on Saturn with an abundance at least equal to the solar P/H value, and probably enhanced by about a factor of 2. No evidence is found for gaseous or solid NH3 on Saturn throughout this spectral region, and upper limits to several other molecules (H2O, HCN, SiH4, and GeH4) are determined. Frequent comparisons of the spectral data for Saturn with observations and interpretations of IR studies of Jupiter show that these two planetary atmospheres are chemically similar, with major observational differences accounted for by reduced H2O and NH3 abundances in Saturn's colder atmosphere.
Phosphine photochemistry in the atmosphere of Saturn
The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.
Detection of the J-10 Manifold of the Pure Rotational Band of Phosphine on Saturn
The detection of the J = 10 manifold of the pure rotational band of PH3 on Saturn is reported. The observations were made from the far-infrared cooled grating spectrometer. The wavelengths and observed brightness temperatures for the full disk plus rings are 89 + or - 3 K at 97.04 micrometer, 77 + or - 3 K at 102.72 micrometer, 77 + or - 3 K at 102.94 micrometer, and 83 + or - 3 K at 105.12 micrometers. The points of 97.04 and 105.12 micrometers establish the continuum level and the two points near 103 micrometers measure the depth of the PH3 manifold. After the flux due to the rings is subtracted, the depth of the feature is 16 + or - 6 K relative to the nearby 102 K continuum. These results are compared to theoretical models which parameterize the PH3 mixing ratio as x = x sub zero (P/P sub zero)(alpha) for P P sub zero and as x = x sub zero for P or = P, where P is the total pressure and alpha = H/h is the ratio of the dynamical scale height (H) and the scale height for decreasing the PH3 mixing ratio (h). The parameters x sub zero, P sub zero, and h were varied, as well as the H/He mixing ratio and the pressure-temperature profile. The data are well fitted using pressure-temperature profiles. The preferred values of h, P sub zero, and x sub zero imply that there is little or no PH3 above the thermal inversion and that the mixing ratio below the inversion is consistent with PH3 being 1 to 4 times overabundant relative to the solar P/H ratio.
Mass spectrometric studies of phosphine pyrolysis and OMVPE growth of InP
The mechanism of PH3 decomposition was studied by using D2 as a carrier gas and analyzing the reaction products with a mass spectrometer. The effects of InP and silica surfaces were investigated. The only gaseous product below 600 C is H2. Since any gas-phase H atoms would produce HD, the reaction occurs entirely on the surface. The slow step is the unimolecular removal of the first hydrogen atom, with an activation energy of 36.0 kcal/mole on InP surfaces. The reaction on InP is first-order for PH3 concentrations as high as 15 percent, so the surface is not saturated at those conditions. When trimethylindium (TMIn) is added to the gas mixture, the mechanism changes dramatically, probably proceeding via an unstable intermediate adduct of TMIn and PH3 which eliminates CH4 upon formation. This concerted reaction lowers the pyrolysis temperatures of both PH3 and TMIn.
Vertical transport in the Jovian upper troposphere: insights from phosphine submillimeter observations
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