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1.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers 下载免费PDF全文
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
2.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
3.
Sébastien Lemaire Giuliano Giambastiani Barbara Pacini Giovanni Poli 《Journal of organometallic chemistry》2003,687(2):291-300
A new type I palladium-catalyzed pseudo-domino process is developed, in which a single Pd-based catalytic system promotes two mechanistically unrelated, sequential catalytic cycles in chronologically distinct order. Suitable precursors undergo an allylic alkylation and a Heck coupling in sequence, affording polycondensed pyrrolidone derivatives. Depending on the starting precursors, intra/inter or doubly intramolecular processes can be obtained. The allylic alkylation process takes place always very smoothly. On the other hand, the Heck coupling turns out to be rather difficult either when the process is intermolecular, or when an intramolecular process generates polycondensed structures featuring three fused bonds connected to a common carbon atom. In such difficult cases, use of the Herrmann-Beller phosphapalladacycle allowed to catalyze the coupling. This study demonstrates also that allylic alkylations can be catalyzed by the Herrmann-Beller phosphapalladacycle. 相似文献
4.
Abstract— Partial recovery of ultraviolet-damaged denatured transforming DNA from Haemophilus influenzae , was obtained by exposing irradiated denatured DNA to nitrous acid and assaying transforming activity. This reactivation was affected by the time of incubation with nitrous acid. 相似文献
5.
In this contribution we present new data resulting from the analysis of concentration patterns of mixed juvenile fragments ejected by a highly explosive volcanic eruption that occurred on Salina Island (Aeolian Islands, Italy) and our aim is to identify the fluid-dynamic regime characterizing the magma mixing process. Concentration patterns are studied by calculating the power spectrum of concentration variability along transects crossing the magma mixing structures. Results indicate that the slope of power spectrum has an average value of about −5/3, according to Kolmogorov law of turbulence, and suggest that the magma mixing process, in the studied conditions, can be approximated by considering the passive scalar mixing hypothesis in homogeneous isotropic turbulent flow. These results represent a first step towards a better understanding of magma mixing processes associated to highly explosive volcanic eruptions and this first step is taken by studying concentration patterns in volcanic rocks by coupling petrological and non-linear dynamics methods. 相似文献
6.
D. Kast A. Jungclaus K.P. Lieb M. Górska G. de Angelis P.G. Bizzeti A. Dewald C. Fahlander H. Grawe R. Peusquens M. De Poli H. Tiesler 《The European Physical Journal A - Hadrons and Nuclei》1998,3(2):115-128
In the neutron deficient isotopes 104,105In lifetimes of high spin states in the range from 0.5 ps to 600 ps have been measured in a coincidence recoil distance Doppler
shift (RDDS) experiment. By combining the Doppler shift attenuation (DSA) and RDDS methods at few μm flight distances, the
problem of delayed feeding has been avoided and very short lifetimes in the range 0.5–0.8 ps have been determined. Shell model
calculations with strong restrictions for the neutron orbitals reveal good agreement with experimental level energies and
still fair agreement for most measured B(M1) and B(E2) values.
Received: 30 June 1998 相似文献
7.
S. O. Olabanji O. R. Omobuwajo D. Ceccato M. C. Buoso M. De Poli G. Moschini 《Journal of Radioanalytical and Nuclear Chemistry》2006,270(3):515-521
Summary Analysis of thirteen medicinal plants of various biological activities commonly used in South-western Nigeria was carried
out using PIXE technique. Nine of these plants are anti-cancer while four are antimicrobial. PIXE measurements were carried
out using collimated proton beams delivered by the 2. 5 MV AN 2000 Van de Graaff accelerator at the Istituto Nazionale di
Fisica Nucleare (INFN), (LNL) Legnaro, (Padova), Italy. The results showed the presence of twenty three different elements
in the plants and none of them contains any toxic heavy metals. Only Chenopodium ambrosioides showed detectable levels of selenium which is considered important in cancer prevention. 相似文献
8.
Venturi F. Sangiorgi E. Luryi S. Poli P. Rota L. Jacoboni C. 《Electron Devices, IEEE Transactions on》1991,38(3):611-618
Carrier transport across the semiconductor space-charge region of a silicon triangular barrier diode was investigated by a Monte Carlo simulation. Oscillations of the electron mean kinetic energy are observed as a function of position along the uphill slope of the barrier under bias. At a given point on the uphill slope, the energy distribution function shows an oscillatory behavior, with a periodicity corresponding to the optical phonon energy. These oscillations are shown to be due to the nonequilibrium dynamics of the electron interaction with optical phonons in the situation when other inelastic electron scattering processes are negligible. The energy oscillations are superimposed on a smooth cooling of the distribution in the transport toward the top of the barrier, as current flows through the system. A comparison with the thermionic theory quantifies the importance of nonequilibrium effects in short-range electronic transport 相似文献
9.
Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and subsequent hydrolysis to give PhP(H)CH(2)CH(Ph)NHPh (mixture of two diastereomers L(4A) and L(4B)). The latter reacts with diethylamine and formaldehyde to afford the L(5) diastereomeric mixture. Complexes RhCl(CO)(L) (L = L(3A), 1(A); L(3B), 1(B); L(5A/B), 2(A/B)) were obtained by reaction of [RhCl(CO)(2)](2) and the appropriate ligand or ligand mixture. Complexes 1(A), 1(B), and 2(A) have been isolated in pure form and characterized by classical techniques and by single-crystal X-ray diffraction. All structures exhibit a bidentate kappa-P,kappa-N(NHPh) mode similar to the complex containing L(1). While complexes 1(A) or 1(B) are stable in CDCl(3) solution, complex 2(A) slowly converts to its diastereomer 2(B). This unexpected epimerization appears to take place by inversion at the Rh-coordinated P center, an apparently unprecedented phenomenon. A mechanism based on a reversible P-C bond oxidative addition is proposed. The influence of the pendant nitrogen function of the diaminophosphines L(3A) and L(5A/B) on the rhodium catalytic activity in styrene hydroformylation has been examined and compared to that of the aminophosphines L(1) or L(2). The observed trends are related to the basicity of the dangling amine function and to its proximity to the metal center. 相似文献
10.
The preparative synthesis of a 3-acetamido-3,6-dideoxy-d-galactopyranose N-phenyl-trifluoroacetimidate donor has been accomplished using as key step a silica gel mediated cyclization of an epoxytrichloroacetimidate, while other more conventional routes to aminosugars failed. Test glycosylations with the N-phenyl-trifluoroacetimidate donor are also reported. 相似文献