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51.
Feller M Karton A Leitus G Martin JM Milstein D 《Journal of the American Chemical Society》2006,128(38):12400-12401
The reaction of the cationic (PNP)Ir(I)(cyclooctene) complex (1) (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) with 2-butanone or 3-pentanone results in the selective, quantitative activation of a beta C-H bond, yielding O,C-chelated complexes. Calculations show that the selectivity is both kinetically (because of steric reasons in the rate determingin step (RDS)) and thermodynamically controlled, the latter as a result of carbonyl oxygen coordination in the product. The RDS is formation of the eta2-C,H intermediates from the complexed ketone intermediates. Water has a strong influence on the regioselectivity, and in its presence, reaction of 1 with 2-butanone gives also the alpha terminal C-H activation product. Computational studies suggest that water can stabilize the terminal alpha C-H activation product by hydrogen bonding, forming a six-membered ring with the ketone, as experimentally observed in the X-ray structure of the acetonyl hydride aqua complex. 相似文献
52.
Sterically demanding secondary phosphines and phosphides react with (THF)B(C(6)F(5))(3) (THF = tetrahydrofuran) to give the THF ring-opened compounds [R(2)PHC(4)H(8)OB(C(6)F(5))(3)] and [Mes(2)PC(4)H(8)OB(C(6)F(5))(3)Li(THF)(2)] (Mes = C(6)H(2)Me-2,4,6). These reactions also occur consecutively to give the double THF ring-opened compounds [Mes(2)P(C(4)H(8)OB(C(6)F(5))(3))(2)][Li(THF)(4)] and [t-Bu(2)P(C(4)H(8)OB(C(6)F(5))(3))(2)Li]. 相似文献
53.
Molev G Bravo-Zhivotovskii D Karni M Tumanskii B Botoshansky M Apeloig Y 《Journal of the American Chemical Society》2006,128(9):2784-2785
The first tricoordinate fluorosilylenoid, (t-Bu2MeSi)2SiFLi.3THF (1), was synthesized, and its X-ray molecular structure was determined. 1 was synthesized in 40% yield by a bromine-lithium exchange reaction in THF of the corresponding fluorobromosilane with t-Bu2MeSiLi. 1 is best described as an R2SiF- anion attracted to a (Li.3THF)+ cation with a small contribution of resonance structure that consists of a silylene fragment and FLi.3THF. 1 reacts as a nucleophile with MeCl, PhH2SiCl, H2O, and MeOH, as an electrophile with MeLi, and as a silylene with Li (or t-BuLi) and Na, yielding alpha-lithium and alpha-sodium silyl radicals, respectively. Either photolysis or thermolysis of 1 yields the corresponding disilene R2Si=SiR2 (R = t-Bu2MeSi), probably via dimerization of R2Si:. 相似文献
54.
A series of eight dimethoxybenziporphyrins were prepared in three steps from 1,3-dimethoxybenzene or 2,6-dimethoxytoluene. Dibromination, followed by lithium-halogen exchange and reaction with benzaldehyde gave dicarbinol intermediates. These reacted with pyrrole and aryl aldehydes in the presence of BF3.Et2O in chloroform, followed by oxidation with DDQ, to give the benziporphyrins in 15-25% yield. These compounds readily gave nickel(II) and palladium(II) organometallic derivatives and could be selectively reduced with sodium borohydride to give unstable benziphlorins. Regioselective oxidation with silver acetate afforded the related 22-acetoxybenziporphyrins in 52-64% yield. The dimethoxybenziporphyrins showed chemical shifts by proton NMR spectroscopy that were consistent with weakly diatropic macrocycles. However, addition of TFA gave dications that showed far more significant shifts that are attributed to the presence of a more substantial diatropic ring current. The internal CH for 11H2(2+) was observed at 3.5 ppm, but this effect was diminished for the 3-methylbenziporphyrins 12H2(2+) where this resonance appears at 4.7 ppm. Even in the absence of the methoxy substituents, the dication derived from tetraphenylbenziporphyrin 8H2(2+) shows an upfield shift for this resonance to 5.5 ppm. The dications of the 22-acetoxybenziporphyrins also show similar effects despite the presence of an internal ester moiety. These results demonstrate that a spectrum of diatropic character can manifest even in highly crowded benziporphyrin derivatives. 相似文献
55.
Jernigan FE Sieracki NA Taylor MT Jenkins AS Engel SE Rowe BW Jové FA Yap GP Papish ET Ferrence GM 《Inorganic chemistry》2007,46(2):360-362
The recently synthesized 3-tert-butyl-5-methyl-1,2,4-triazole reacted with KBH4 to give the new potassium tris(3-tert-butyl-5-methyl-1,2,4-triazolyl)borate K(Ttz(tBu,Me)) ligand. Ttz(tBu,Me) formed a four-coordinate (Ttz(tBu,Me))CoCl complex and five-coordinate (Ttz(tBu,Me))CoNO3 and (Ttz(tBu,Me))ZnOAc complexes. When these complexes were compared to their Tp(tBu,Me) analogues, it was found that Ttz(tBu,Me) resulted in negligible steric differences. K(Ttz(tBu,Me)) is more water-soluble than K(Tp(tBu,Me)), so bulky tris(triazolyl)borate ligands should lead to functional models for enzyme active sites in an aqueous environment and the creation of water-soluble analogues of Tp catalysts. 相似文献
56.
Briggs TF Winemiller MD Collum DB Parsons RL Davulcu AH Harris GD Fortunak JM Confalone PN 《Journal of the American Chemical Society》2004,126(17):5427-5435
The 1,2-addition of lithium phenylacetylide (PhCCLi) to quinazolinones was investigated using a combination of structural and rate studies. (6)Li, (13)C, and (19)F NMR spectroscopies show that deprotonation of quinazolinones and phenylacetylene in THF/pentane solutions with lithium hexamethyldisilazide affords a mixture of lithium quinazolinide/PhCCLi mixed dimer and mixed tetramer along with PhCCLi dimer. Although the mixed tetramer dominates at high mixed aggregate concentrations and low temperatures used for the structural studies, the mixed dimer is the dominant form at the low total mixed aggregate concentrations, high THF concentrations, and ambient temperatures used to investigate the 1,2-addition. Monitoring the reaction rates using (19)F NMR spectroscopy revealed a first-order dependence on mixed dimer, a zeroth-order dependence on THF, and a half-order dependence on the PhCCLi concentration. The rate law is consistent with the addition of a disolvated PhCCLi monomer to the mixed dimer. Investigation of the 1,2-addition of PhCCLi to an O-protected quinazolinone implicates reaction via trisolvated PhCCLi monomers. 相似文献
57.
RA Martin HL Twyman GJ Rees JM Smith ER Barney ME Smith JV Hanna RJ Newport 《Physical chemistry chemical physics : PCCP》2012,14(35):12105-12113
The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 < r (?) < 3 region via the difference method has enabled all the nearest neighbour correlations to be deconvolved. The diffraction data provides the first direct experimental evidence of split Na-O nearest-neighbour correlations in these melt quench bioactive glasses, and an analogous splitting of the Li-O correlations. The observed correlations are attributed to the metal ions bonded either to bridging or to non-bridging oxygen atoms. (23)Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design. 相似文献
58.
Self-assembly of a binary monolayer of charged particles is modeled using molecular dynamics and statistical mechanics. The equilibrium phase diagram for the system has three distinct phases: an ionic crystal; a geometrically ordered crystal with disordered charges; and a fluid. We show that self-assembly occurs near the phase transition between the ionic crystal and the fluid, and that the rate of ordering is sensitive to the applied pressure. By assuming an Arrhenius form for the rate of ordering, an optimality condition for the temperature and pressure is derived that maximizes the rate. Using the Clausius-Clapeyron equation, the optimal point on the phase boundary is expressed in terms of the thermodynamic changes in state variables across the boundary. The predicted optimal temperature and pressure conditions are in good agreement with numerical simulations and result in self-organization rates five times that of a simulation without applied pressure. 相似文献
59.
The rhodium-catalyzed regioselective amination of tertiary allylic trichloroacetimidates with unactivated aromatic amines is a direct and efficient approach to the preparation of α,α-disubstituted allylic aryl amines in good yield and with excellent regioselectivity. This method is applicable to a variety of unactivated primary and secondary amines and allows for the preparation of reverse prenylated indoles in two steps. 相似文献
60.
Mumin AM Barrett JW Dekaban GA Zhang J 《Journal of colloid and interface science》2011,353(1):156-162
In this paper, foam-structured fluorescent mesoporous silica nanoparticles (FMSNs) are produced in a sol-gel method with the introduction of a phosphonate functional group. It is found that the phosphonate functionalized FMSNs with the foam structure minimizes the aggregation of FMSNs in solution. The average particle size of the FMSNs without and with phosphonate functionalization is 46.3 ± 5 nm and 60.5 ± 8 nm in diameter, respectively. The latter one exhibits higher fluorophore loading capacity (~67 ± 2.5%). The excitation wavelength (λ(ex)) of FMSNs is observed at 526 nm, approximate 12 nm larger in the Stoke-shift compared to the free organic dye at 494/514 nm. Furthermore, the photostability of the hydrophobic fluorophore is greatly improved by the FMSNs with the foam structure. In addition, the dose-dependent nature of FMSN uptake is assessed for the immune cells, the bone marrow-derived dendritic immune cells (BMDCs). Our results indicate that approximately 42% of BMDCs are able to take up foam-structured FMSNs (>5 μg/ml) without decreasing the viability of BMDCs. Thus, the phosphonate functionalized FMSNs with the foam structure are suitable to be used for many biomedical applications, especially in cell tracking. 相似文献