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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.
Gregorio Falqui 《Reports on Mathematical Physics》2002,50(3):395
We formulate and discuss a reduction theorem for Poisson pencils associated with a class of integrable systems, defined on bi-Hamiltonian manifolds, recently studied by Gel'fand and Zakharevich. The reduction procedure is suggested by the bi-Hamiltonian approach to the separation of variables problem. 相似文献
4.
Jean-Pierre Dedieu Gregorio Malajovich Mike Shub 《Foundations of Computational Mathematics》2005,5(2):145-171
We prove a linear bound on the average total curvature of the
central path of linear programming theory in terms of the number
of independent variables of the primal problem, and independent of
the number of constraints. 相似文献
5.
Rinaldo M. Colombo Alessandro Groli 《Journal of Mathematical Analysis and Applications》2004,291(1):82-99
In the present note, the theory of shift differentiability for the Cauchy problem is extended to the case of an initial boundary value problem for a conservation law. This result allows to exhibit an Euler-Lagrange equation to be satisfied by the extrema of integral functionals defined on the solutions of initial boundary value problems of this kind. 相似文献
6.
Enrique Saldívar‐Guerra Jos Bonilla Gregorio Zacahua Martha Albores‐Velasco 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):6962-6979
Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (kh)]. At higher TEMPO concentrations ([N?] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition kad, also becomes relevant. From previous experimental data and simulations, initial estimates of kh ≈ 1 and kad ≈ 6 × 10?7 L mol?1 s?1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression kth[M]3 (where [M] is the monomer concentration and kth is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006 相似文献
7.
Carolina de Gregorio Lemont B. Kier Lowell H. Hall 《Journal of computer-aided molecular design》1998,12(6):557-561
A structure-activity analysis of a series of steroids binding to corticosteroid-binding globulin was made using the electrotopological state index for each atom in the molecule. Two indices were found to correlate well with the binding affinity. The indices encode structural characteristics in the A and the D rings of the steroids in the study. One of the indices was formulated as the difference between two indices in the A ring. The two were not intercorrelated, suggesting that the composite index signals the influence of structure changes in or near the A ring that can be monitored by the composite index. This is a new observation using this structure-activity method. It is suggested that this model makes some contributions towards detection of the pharmacophore. 相似文献
8.
Antolín R Borge G Posada T Raposo JC Seara I Etxebarria N 《Journal of AOAC International》2004,87(5):1218-1223
A validation study was carried out in order to evaluate the efficiency of inductively coupled plasma-optical emission spectrometry (ICP-OES) for the analysis of minor elements (manganese, chromium, copper, iron, and titanium) in aluminium alloys. Aluminium casting samples were obtained by adding compressed powder compacts of each alloying element and aluminium (minitablets) to aluminum baths in a laboratory crucible furnace. Digestion of solid samples was performed using concentrated HCI and H202 35% (v/v) previous to analysis by ICP-OES without any matrix separation. This solution-based method was validated considering direct current arc spectrometry as the reference method based on direct analysis without any pretreatment of the solid samples considered. Univariate statistical procedures were carried out, for which precision <3% and trueness of the analytical results were taken into account. 相似文献
9.
Gregorio Snchez Francisco Ruiz Joaquín Garcia M. Ramírez Carmen de Arellano Gregorio Lpez 《Helvetica chimica acta》1997,80(8):2477-2485
The hydroxo complex (Bu4N)2[Ni2(C6F5)4(μ-OH)2]reacts with 2,3,4,5,6-pentafluoro benzenamine (C6F5-NH2), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC6H4, 4-MeOC6H4), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu4N)2[Ni2(C6F5)4(μ-C6F5NH)2] ( 1 ) and (Bu4N)2[{Ni(C6F5)2} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu4N[Ni(C6F5)2(ArN3Ar)] ( 3 – 5 ), Bu4N[Ni(C6F5)2(pyNPh)] ( 6 ), and Bu4N[Ni(C6F5)2(pyCONPh)] ( 7 ). The hydroxo.complex (Bu4N)2[{Ni(C6F5)2-(μ-OH)}2] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, 1H and 19F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu4N)2[{Ni(C6F5)2}2(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°. 相似文献
10.
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