Plasma fluorination of polyolefins

ESCA and contact angle measurements were used to characterize the surfaces of Polyethylene and polypropylene films exposed to SF₆, CF₄, and C₂F₆ plasmas. None of these gases polymerized in the plasma. However, all plasma treatments grafted fluorinated functionalities directly to the polymer surfaces. SF₆ plasmas graft fluorine atoms to a polyolefin surface. CF₄ plasmas also react by a mechanism dominated by fluorine atoms, but with some contribution from CF_x-radical reactions. Although C₂F₆ does not polymerize, the mechanism of grafting is still dominated by the reactions of CF_x radicals. For all gases studied, the lack of polymerization is attributed to competitive ablation and polymerization reactions occurring under conditions of ion bombardment.     

Synthesis of spiro-fused (C5)-isoxazolino-(C4)-pyrazolones (1-oxa-2,7,8-triazaspiro[4,4]-2,8-dien-6-ones) via 1,3-dipolar cycloaddition and cycloelimination

An efficient and selective method for the synthesis of spiro-fused (C5)-isoxazolino-(C4)-pyrazolones (C) is reported. The process consists of utilizing the Baylis-Hillman reaction-or a quicker, stepwise MAC procedure-to give I followed by 1,3-dipolar cycloaddition and Swern oxidation to give beta-ketoesters H, which were condensed with hydrazine derivatives to provide hydrazones that underwent cycloelimination. These novel spiro-fused (C5)-isoxazolino-(C4)-pyrazolones were confirmed by spectroscopic analysis as well as single-crystal X-ray of 5. We also concluded that all condensations/cycloeliminations, except with hydrazine itself, were more effective with catalysts or higher reaction temperatures. For example, TiCl(4) was an efficient catalyst for hydrazone formation and cycloelimination with methylhydrazine, while phenyl-, benzyl-, and (4-methoxyphenyl)hydrazine reacted effectively without catalyst in refluxing xylene.     

Energetics of the Preyssler anion's molecular orbitals: quantifying the effect of the encapsulated-cation's charge

The ground state electronic properties of metal-exchanged Preyssler heteropolyoxoanions [M(n+)P(5)W(30)O(110)](n-15), in which the encapsulated M(n+) ions are the spherical, diamagnetic ions Na(+), Ca(2+), Sr(2+), Y(3+), La(3+) and Th(4+), are studied using a combination of electrochemical, optical, and NMR experiments. We have designed experiments that focus on the influence of the charge (n) of the encapsulated cations, which themselves have no redox response, and its effect upon the W-O framework MOs. As n increases, the cluster anions accept electrons into their LUMOs with increasing ease, and their lowest-energy LMCT bands reveal a corresponding blue shift, which is indicative of an increase of the LUMO-HOMO energy splitting with increasing n. (183)W NMR spectra are used to identify the atomic origin of the LUMO states, which are shown to be composed primarily of orbitals from the ring of 5 W atoms near M(n+). The cation charge correlates directly and linearly with the half-wave potentials of the first redox couples, the LMCT band energies, and the W chemical shifts. We have combined this suite of experimental results to construct an energy level diagram of the frontier MOs for the Preyssler cluster anions. In so doing, we provide a fundamental perspective that is not otherwise available on the cation's role with specific regard to the electronic behavior of the W-O orbitals. These results are expected to provide benchmarking information as theorists begin to study these large POM systems.     

Observation of an unprecedented Cu Bis-His site: crystal structure of the H129V mutant of nitrite reductase

Copper nitrite reductases contain both an electron-transfer type 1 Cu site and a catalytic type 2 Cu site. We have mutated one of the type 2 copper ligating histidines to observe the effect on catalytic turnover. This mutation has created a unique site where Cu is ligated by 2 His Nepsilon2 atoms alone.     

Mechanistic studies of nickel(II) alkyl agostic cations and alkyl ethylene complexes: investigations of chain propagation and isomerization in (alpha-diimine)Ni(II)-catalyzed ethylene polymerization

The synthesis of a series of (alpha-diimine)NiR(2) (R = Et, (n)Pr) complexes via Grignard alkylation of the corresponding (alpha-diimine)NiBr(2) precursors is presented. Protonation of these species by the oxonium acid [H(OEt(2))(2)](+)[BAr'(4)](-) at low temperatures yields cationic Ni(II) beta-agostic alkyl complexes which model relevant intermediates present in nickel-catalyzed olefin polymerization reactions. The highly dynamic nature of these agostic alkyl cations is quantitatively addressed using NMR line broadening techniques. Trapping of these complexes with ethylene provides cationic Ni alkyl ethylene species, which are used to determine rates of ethylene insertion into primary and secondary carbon centers. The Ni agostic alkyl cations are also trapped by CH(3)CN and Me(2)S to yield Ni(R)(L)(+) (L = CH(3)CN, Me(2)S) complexes, and the dynamic behavior of these species in the presence of varied [L] is discussed. The kinetic data obtained from these experiments are used to present an overall picture of the ethylene polymerization mechanism for (alpha-diimine)Ni catalysts, including effects of reaction temperature and ethylene pressure on catalyst activity, polyethylene branching, and polymer architecture. Detailed comparisons of these systems to the previously presented analogous palladium catalysts are made.     

Surfactant displacement of human serum albumin adsorbed on loosely packed self-assembled monolayers: cetyltrimethylammonium bromide versus sodium dodecyl sulfate

The surfactants sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) displace human serum albumin (HSA) from loosely packed self-assembled monolayers (SAM) of hydrophobic alkyl chains by different means. Removal of HSA is of interest because previous work has suggested that the adsorption of HSA to such loosely packed SAMs may be sufficiently tenacious to offer opportunities for surface passivation. While HSA remains on the surface after exposure to SDS and rinsing, no protein remains after exposure to CTAB and rinsing. X-ray reflectivity and X-ray photoelectron spectroscopy measurements indicate that CTAB molecules remain interdigitated in the loosely packed SAM after rinsing, suggesting that CTAB is more effective in removing the HSA because it interacts more strongly with the SAM.     

The observation of a large gauche preference when 2-fluoroethylamine and 2-fluoroethanol become protonated

The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference.     

Ligand-modulated stereo- and regioselective tandem addition reactions of rhenium-bound naphthalene

A series of complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe(3), the reaction of the eta(2)-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine, N,N-dimethylaminopyridine, N-methylimidazole, or NH(3) the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H(+), D(+)) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. One-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield.     

Substituenteneffekte auf die C–C-Bindungsstärke, 8. Standardbildungsenthalpien und Spannungsenthalpien von 1,1,2,2-Tetraethylethylenglykol-dimethylether und D,L-1,2-Dimethyl-1,2-diphenylethylenglykol-dimethylether

Effects of Substituents on the Strength of C - C Bonds, 8¹. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol ^-1, s. d. in parentheses) ΔH°_c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔH^v = 14.3 (± 0.3) and the heat of sublimation of 2 ΔH^sub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°_t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (_s) of 15.9 and 8.0 kcal mol^-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group.