(OXO)(Phosphine)Ruthenium(IV) Complexes: Oxygen Atom Transfer in the Oxidation of Olefins,Sulfides, Sulfoxides,and Free Phosphines

Kinetic and mechanistic studies of the oxidation of olefins, sulfides, and sulfoxides by [Ru^IV(bpy)₂(O)- (PR₃)](ClO₄)₂ (bpy = 2,2′-bipyridine; R = ethyl or phenyl) complexes have been conducted in both methylene chloride and acetonitrile. In all cases, the rate law shows a first-order dependence on both the concentration of (oxo)ruthenium(IV) species and the target substrate. In addition, product distributions of substrate oxidation exhibit a strong dependence on both the particular phosphine ligand and the solvent utilized in the experiment. On the basis of labelling experimcnts and kinetic evidence, a mechanism is proposed involving a two-electron, oxygen atom insertion into the target substrate. Notably, an (oxidized substrate)ruthenium(II) complex has been isolated and characterized for the oxidation of styrene by the (oxo)(triethylphosphine)ruthenium(IV) complex, where a cyclic voltammogram of this complex displays one quasi-reversible Ru(III)/Ru(II) couple with an E_1/2 = 1.24 V vs SSCE. Kinetic analysis of styrene oxidation indicates that the formation of benzaldehyde from styrene does not occur simply by two sequential two-electron steps. In this regard, alternative mechanisms are discussed.     

Oriented O(3P2), Ne(3P2), and He(3S1) atoms emerging from a bent magnetic guide

We describe our observation of strongly oriented total electronic angular momentum J in O(³P₂), Ne(³P₂), and He(³S₁) atoms emerging from a bent magnetic multipole guide, as measured by resonant multiphoton ionisation. This was contrary to our expectation because no additional (uniform) magnetic fields were applied to orient the atoms behind the exit of the guide. Two- and three-photon ionisation techniques were employed to determine the degree of J polarisation, from which we infer that atoms become oriented as a result of a combination of weak fringe fields, possible stray fields, and the fact that molecular beam packets do not oscillate around the geometric center of the bent multipole guide. We conclude that similar effects may exist in other, related experiments and that a detailed characterisation of the degree of orientation is required prior to any study of chemical dynamics or spectroscopy. This paper should serve as a warning for anybody using similar devices not to assume isotropic angular momentum distributions of atoms and molecules emerging from a magnetic guide or a decelerator, particularly when it is bent; whenever possible, the possibility for a J anisotropy should be experimentally checked.     

Decatungstate as a direct hydrogen atom transfer photocatalyst for synthesis of trifluromethylthioesters from aldehydes

We have developed a versatile, mild protocol for trifluoromethylthiolation reactions of aldehydes with catalysis by a decatungstate hydrogen atom transfer photocatalyst under redox-neutral conditions. The protocol is highly selective, operationally simple, and compatible with a wide array of sensitive functional groups. It can be used for late-stage functionalization of bioactive molecules, which makes it convenient for drug discovery.     

Hyperbranched block copolymer from AB2 macromonomer: Synthesis and its reaction‐induced microphase separation in epoxy thermosets

In this contribution, we reported the synthesis of a hyperbranched block copolymer composed of poly(ε‐caprolactone) (PCL) and polystyrene (PS) subchains. Toward this end, we first synthesized an α‐alkynyl‐ and ω,ω′‐diazido‐terminated PCL‐b‐(PS)₂ macromonomer via the combination of ring‐opening polymerization and atom transfer radical polymerization. By the use of this AB₂ macromonomer, the hyperbranched block copolymer (h‐[PCL‐b‐(PS)₂]) was synthesized via a copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition (i.e., click reaction) polymerization. The hyperbranched block copolymer was characterized by means of ¹H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Both differential scanning calorimetry and atomic force microscopy showed that the hyperbranched block copolymer was microphase‐separated in bulk. While this hyperbranched block copolymer was incorporated into epoxy, the nanostructured thermosets were successfully obtained; the formation of the nanophases in epoxy followed reaction‐induced microphase separation mechanism as evidenced by atomic force microscopy, small angle X‐ray scattering, and dynamic mechanical thermal analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 368–380     

Well‐controlled ATRP of 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate for high‐density click functionalization of polymers and metallic substrates

The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido‐bearing methacrylate monomers (e.g., 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 °C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well‐defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number‐average molecular weights (M_n) up to 22 kDa with narrow polydispersity (PDI < 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface‐initiated ATRP (SI‐ATRP), and effectively functionalized the azide‐terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well‐controlled ATRP of azido‐bearing methacrylates and subsequent facile high‐density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1268–1277     

Fluorinated star‐shaped block copolymers: Synthesis and optical properties

Tetrakis(4‐(1‐bromoethyl)phenyl)silane is synthesized and utilized to initiate the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to generate bromo‐terminated four‐armed PMMA macroinitiators, which further initiate the ATRP of methylacryloyloxyl‐2‐hydroxypropyl perfluorooctanoate (FGOA) to create fluorinated star‐shaped block copolymers PMMA‐b‐poly(FGOA)s with fluorine content ranging from 0 to 31.7 wt %. The polymerizations are well controlled with the polydispersity indices <1.30. The polymers readily dissolve in common organic solvents and show good film‐formation. Compared with the nonfluorinated sample, the fluorinated films exhibit significantly increased water contact angles owing to the enrichment of fluorine on the surface. The enhanced hydrophobicity is advantageous for the optical stability when the devices work under a moist environment. Moreover, the films possess high thermo‐optic coefficients, tunable refractive indices, and extremely low birefringence coefficients because of the presence of bulky and rigid tetraphenylsilane core and star‐shaped topological structure, showing potential application in optical waveguide devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1969–1977     

Synthesis of diblock copolymers by combination of organocatalyzed ring‐opening polymerization and atom transfer radical polymerization using trichloroethanol as a bifunctional initiator

This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and ¹H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 563–569     

Development of resonance‐enhanced multiphoton ionization SNMS for state‐selective detection of sputtered atoms under low‐energy ion irradiation

An instrument for a sputtered neutral mass spectrometry with a quadrupole mass spectrometer (QMS) by resonance‐enhanced multiphton ionization method is developed to study sputtered neutrals emission phenomena under ion irradiation in a low‐energy region. We have prepared a pulsed primary ion beam and an ion counting system, and have optimized the operation parameter including a sample bias, energy analyzer voltages, pulsed timing of laser and ion beam, etc. A yield ratio of the lowest‐lying excited state a⁵S₂ to the ground state a⁷S₃ for sputtered Cr atoms has been measured as a function of incident energy of Ar⁺ and O₂⁺ down to 600 eV using a polycrystalline Cr sample. The yield ratio has become a constant value for the Ar⁺ incidence, while it has exponentially increased below 1 keV for the O₂⁺ incidence. It is found that the internal energy distribution of sputtered Cr atoms has been significantly influenced by oxygen density at the surface. Copyright © 2011 John Wiley & Sons, Ltd.     

Decay rates of select magnetic quadrupole transitions in helium

Using a set of explicitly correlated trial wavefunctions that describe the three lowest singlet and triplet states of the helium atom with symmetry S, P, and D, we calculate the decay rates for all possible magnetic quadrupole (M2) transitions: m³P₂→n¹S₀, m¹P₁→n³S₁, m³D₃→n¹P₁, and m¹D₂→n³P₂. Our values are in excellent agreement with the best results in the literature. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Recent Progress on Transition Metal Catalyst Separation and Recycling in ATRP

Atom transfer radical polymerization (ATRP) is a versatile and robust tool to synthesize a wide spectrum of monomers with various designable structures. However, it usually needs large amounts of transition metal as the catalyst to mediate the equilibrium between the dormant and propagating species. Unfortunately, the catalyst residue may contaminate or color the resultant polymers, which limits its application, especially in biomedical and electronic materials. How to efficiently and economically remove or reduce the catalyst residue from its products is a challenging and encouraging task. Herein, recent advances in catalyst separation and recycling are highlighted with a focus on (1) highly active ppm level transition metal or metal free catalyzed ATRP; (2) post‐purification method; (3) various soluble, insoluble, immobilized/soluble, and reversible supported catalyst systems; and (4) liquid‐liquid biphasic catalyzed systems, especially thermo‐regulated catalysis systems.