Mono(phosphine)palladium(0)
complexes, [Pd(η2:η2-C6H10O)(PR3)] (1), catalyze hydrosilylation
of electron-deficient conjugated dienes with HSiPh3. Hydrosilylation
of methyl penta-2,4-dienoate with HSiPh3 catalyzed by [Pd(η2:η2-C6H10O)(PR3)] (R = Me (1a), Et (1b), OEt (1d), O
i
Pr (1e)) proceeds
to give the 1,2-E product in quantitative yield with
exclusive Markovnikov selectivity. In contrast, their triphenylphosphine
and -phosphite analogues, [Pd(η2:η2-C6H10O)(PR3)] (R = Ph (1f), OPh (1g)), mainly produce the 1,4-Z product (1,2-E/1,4-Z = 3/7). The
regioselectivity in the hydrosilylation of methyl 2,4-pentadienoate
is also controlled by organosilanes. Mechanistic studies suggest that
the reaction using a compact and basic mono-phosphorus complex proceeds
by the Chalk–Harrod mechanism involving the reductive elimination
from an (η3-allyl)(silyl)palladium(II). A poor electron-donating
mono-phosphorus ligand such as P(OPh)3 destabilizes a Pd(II)
species and promotes direct reductive elimination to give the 1,4-Z product. On the other hand, a compact and electron-donating
phosphorus ligand, such as PMe3, PEt3, and P(OMe)3, favors to give the more stable (η3-allyl)(silyl)palladium(II)
intermediate by the allyl rotation, followed by reductive elimination
to give the 1,2-E product.
Multicomponent polymer particles with specific morphology are promising materials exhibiting novel functionality which cannot be obtained with single-component polymer particles. Particularly, the preparation of such kinds of polymer particles involving electrically or optically active conjugated polymers with uniform size is a challenging subject due to their intense demands. Here, microspheres of binary polymer blend consisting of poly(4-butyltriphenylamine) (PBTPA)/poly(methyl methacrylate) (PMMA) (1:1 in weight) were produced via a microfluidic emulsification with a Y-shaped microreactor, and a subsequent solvent evaporation method. The flow rate of the dispersed phase (polymer solution) was fixed to 7 µL/min, and 140 or 700 µL/min of the flow rate of the continuous phase (aqueous 0.6 wt % of poly(vinyl alcohol) (PVA) solution) was utilized to produce the dispersion with different diameter. The concentration of dispersed phase was adjusted to 0.1 or 1.0 w/v%. Core-shell, Janus and dumbbell type microspheres were obtained dependent on the flow rate of continuous phase. Incomplete core-shell type microspheres were produced for the blend involving low molecular weight PMMA. Complex Janus and core-shell type microspheres were fabricated by the addition of sodium dodecyl sulfate (SDS) to continuous phase. It is found that final morphologies are strongly dependent on the initial conditions of dispersion including the particle size suggesting that the morphologies are governed by the kinetical factors together with the conventionally accepted thermodynamic ones.
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