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John D Protasiewicz

Publications and source records attributed to John D Protasiewicz.

10 recordsLinked to original sources
PubMed2006

Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations.

A series of phosphaalkenes, E-ArP=C(H)Ar' (Ar = 2,6-Mes2C6H3, Ar' = Ph (1a); Ar = 2,6-Mes2C6H3, Ar' = p-C6H4Br (2a); Ar = 4-Br-2,6-Mes2C6H2, Ar' = Ph (3a); Ar = 4-Br-2,6-Mes2C6H2, Ar' = p-C6H4Br (4a)) have been prepared by phospha-Wittig reactions and characterized. Exposure of these materials either to room light over an extended period of time (days) or to UV light (hours) produced equilibrium mixtures of the E and Z isomers (1b-4b) as indicated by 1H and 31P NMR spectroscopy. The structures of compounds 4a and 4b were determined by single-crystal X-ray diffraction methods. Variable-temperature (1)H NMR studies of 4b indicate hindered rotation about the P-CAr bond, with DeltaH(double dagger) = 13.8 kcal/mol and DeltaS(double dagger) = 1.3 eu. The electronic structures of E- and Z-PhP=C(H)Ph have been examined using density functional theory.

Alkenes↗
PubMed2005

Metal-ion adsorption on carboxyl-bearing self-assembled monolayers covalently bound to magnetic nanoparticles.

Hematite nanoparticles have been functionalized with a self-assembled monolayer of undecanoic acid (UA) by covalent attachment via siloxane groups. The number density of carboxylic/carboxylate groups on the surface was determined by titration, yielding values on the order of 10(14) UA molecules/cm(2) and thus consistent with a closed-packed monolayer. The ability of these functionalized particles to adsorb Cd(2+) in the ppm range was demonstrated using in situ anodic stripping voltammetry.

Adsorption↗
PubMed2004

Conjugated polymers featuring heavier main group element multiple bonds: a diphosphene-PPV.

A new sterically encumbered bifunctional ligand has been developed, and its ability to provide simultaneous stabilization for two low-coordinate phosphorus centers has allowed the synthesis of new hybrid inorganic-organic conjugated materials. The new phosphaalkene polymers have been prepared from a diphospha-Wittig reagent and are exclusively E-configured about the P=C bonds. An unprecedented polymer having diphosphene (-P=P-) units in the polymer main chain is also reported. The soluble polymers were characterized by UV-visible and fluorescence spectroscopy, as well as by 1H and 31P NMR spectroscopy.

Journal Article↗
PubMed2003

Sterically encumbered diphosphaalkenes and a bis(diphosphene) as potential multiredox-active molecular switches: EPR and DFT investigations.

The reduction products of two diphosphaalkenes (1 and 2) and a bis(diphosphene) (3) containing sterically encumbered ligands and corresponding to the general formulas Ar-X=Y-Ar'-Y=X-Ar, have been investigated by EPR spectroscopy. Due to steric constraints in these molecules, at least one of the dihedral angles between the CXYC plane and either the Ar plane or the Ar' plane is largely nonzero and, hence, discourages conformations that are optimal for maximal conjugation of P=X (or P=Y) and aromatic pi systems. Comparison of the experimental hyperfine couplings with those calculated by DFT on model systems containing no cumbersome substituents bound to the aromatic rings shows that addition of an electron to the nonplanar neutral systems causes the X=Y-Ar'-Y=X moiety to become planar. In contrast to 1 and 2, 3 can be reduced to relatively stable dianion. Surprisingly the two-electron reduction product of 3 is paramagnetic. Interpretation of its EPR spectra, in the light of DFT calculations on model dianions, shows that in [3](2)(-) the plane of the Ar' ring is perpendicular to the CXYC planes. Due to interplay between steric and electronic preferences, the Ar-X=Y-Ar'-Y=X-Ar array for 3 is therefore dependent upon its redox state and acts as a "molecular switch".

Journal Article↗
PubMed2003

A fluorescent E-poly(p-phenylenephosphaalkene) prepared by a phospha-Wittig reaction.

A soluble (E)-poly(p-phenylenephosphaalkene) having sterically encumbering ligands has been prepared by a phospha-Wittig reaction. This material exhibits a bathochromic shift with respect to E-PPV and with respect to representative model oligomers. We also report the first fluorescence study of a poly(p-phenylenephosphaalkene) and find that this material exhibits fluorescence, though with modest intensity relative to similarly sized carbon-based analogues.

Journal Article↗
PubMed2003

S-(2-pyridinyl)-1,1,3,3-tetramethylthiouronium hexafluorophosphate. A new reagent for the synthesis of 2-pyridinethiol esters.

[reaction: see text] A new thiouronium-based reagent for the synthesis of 2-pyridinethiol esters under non-nucleophilic conditions from the corresponding carboxylic acids was developed. The resulting procedure enables the preparation of previously unavailable alpha,beta-unsaturated 2-pyridinethiol esters as well as their aliphatic and aromatic counterparts.

Journal Article↗
PubMed2003

Copper(II)-mediated autoxidation of tert-butylresorcinols.

Although copper(II)-mediated oxidation of phenols results in oxidative coupling rather than in oxygenation, it was recently reported that naturally occurring 5-alkylresorcinols undergo oxygenation in the presence of copper(II). To explore the generality of this reaction, the copper(II)-mediated autoxidation of 4-tert-butylresorcinol and 4,6-di-tert-butylresorcinol was investigated and was found to result in direct oxygenation at open activated positions and, at the tert-butyl-substituted positions, in oxygenation with competing loss of (as isobutylene) and 1,2-rearrangement of the tert-butyl group. 5-tert-Butyl-2-hydroxy-1,4-benzoquinone is the major product from both starting materials, and the final product mixture reflects, in part, coupling of metastable initially formed electrophilic and nucleophilic side products. Mechanisms that are consistent with the observed products and control reactions are proposed. The key step appears to be equilibration of a copper(II)-resorcinolate with a charge-transfer radical form that reacts regioselectively with O(2) as prescribed by resonance.

Alkanes↗
PubMed2003

An unusual equilibrium chlorine atom transfer process and its potential for assessment of steric pressure by bulky aryls.

An unusually facile intermolecular chlorine atom transfer process has been discovered between the phospha-Wittig reagents ArP=PMe3 and ArPCl2 (Ar is a sterically hindered aryl group). The atom transfer process is catalyzed by added PMe3. A mechanism is forwarded that is based upon a Me3P/Me3PCl2 couple that allows shuttling of chlorine atoms between ArP groups. This unique transfer process is exploited to evaluate the steric properties of aryl groups via an equilibrium process.

Journal Article↗
PubMed2002

Syntheses and structural characterizations of the unsymmetrical diphosphene DmpP=PMes* (Dmp =2,6-Mes(2)C(6)H(3), Mes* = 2,4,6-(t)Bu(3)C(6)H(2)) and the cyclotetraphosphane [DmpPPPh](2).

The new diphosphene DmpP=PMes* (Dmp = 2,6-Mes(2)C(6)H(3); Mes* = 2,4,6-(t)Bu(3)C(6)H(2), 1) having two different classes of sterically demanding aryls has been prepared and structurally characterized. This structure appears to be the first featuring both types of sterically demanding groups (a meta-terphenyl and Mes*) in a single molecule about a multiply bonded unit. Compound 1 features a P=P bond length of 2.024(13) A. The structure of 1 also allows comparisons to the two previously structurally characterized symmetric diphosphenes DmpP=PDmp and Mes*P=PMes*. The crystal structure of the cyclotetraphosphane [DmpPPPh](2) (3), the product of self-dimerization of the unstable diphosphene DmpP=PPh (2), has been determined. The structure of 3 demonstrates that a single bulky Dmp group is insufficient to prevent dimerization of 2. (31)P NMR data for all three compounds are also reported.

Journal Article↗