It has been demonstrated by means of spectroscopic studies involving cyclizable alkyl halides that lithium dimethylcuprate can react with organic halides by a single electron transfer pathway. 相似文献
The title reduction may lead to very incomplete isotopic substitution as a result of SET intrusion and the related intermediacy of radicals and hydrogen abstraction from the solvent, even though the halogen to be replaced is chlorine. Two examples are reported. In one of them, this mechanism is shown to be induced through five single bonds by an ether substituent separated from the chlorine by a rigid W-chain of saturated carbons. 相似文献
O-Tolyl/benzyl dithiocarbonates, ROCS2Na (R = o-, m-, or p-CH3C6H4–, and –CH2C6H5), were synthesized and characterized. These new ligands reacted with PCl3/POCl3 in refluxing toluene which resulted in the formation of phosphorus(III) and phosphorus(V) tolyl/benzyl dithiocarbonates corresponding to [(ROCS2)nPCl3−n] and [(ROCS2)nPOCl3−n] (R = o-, m-, or p-CH3C6H4–, and –CH2C6H5; n = 1, 2, 3). These pale yellow liquid compounds were characterized by IR, mass, and NMR (1H, 13C, and 31P) spectral studies, which suggest the dithiocarbonate ligands bind in a monodentate mode leading to P–S–C linkages in these derivatives. 相似文献
We study various $\alpha $-decay chains on the basis of the preformed cluster decay model. Our work targets the superheavy elements, which are expected to show extra stability at shell closure. Our computations identify the following combinations of proton and neutron numbers as the most stable nuclei: $Z=112$, $N=161, 163$; $Z=114$, $N=171, 178, 179$; and $Z=124$, $N=194$. We also investigate the alternative of heavy cluster emissions in the decay chain of 301120, instead of $\alpha $ decay. Our study of cluster radioactivity shows that the half-life for 10Be decay in 289114 is larger, indicating enhanced stability at $Z=114$, $N=175$. Similar calculations concerning the emission of $\ ^{14}{\rm C}$ and $\ ^{34}{\rm Si}$ from 301120 find the more stable combinations $Z=114$, $N=173$, and $Z=106$, $N=161$, respectively. From the same parent, 301120, the emission of a $\ ^{49-51}{\rm Ca}$ cluster yielding a $Z=100$, $N=152$ daughter is the most probable. 相似文献
Polygon clipping is of great importance in computer graphics.One of the popular algorithms to clip a polygon is Cohan–Sutherland Hodgeman algorithm which is based on line clipping.Cohan–Sutherland Hodgeman algorithm clips the polygon against the given rectangular clip window with the help of line clipping method.Cohan–Sutherland algorithm requires traversing the polygon in anti clockwise direction(positive orientation).In this work we propose an efficient polygon clipping algorithm against a rectangular clip window.Proposed algorithm uses parametric representation of polygon edges.Using the concept of point clipping,we can find required intersection points of edges of polygon with clip window boundaries.Well suited numerical illustrations are used to explain the proposed polygon clipping method.The proposed algorithm is computationally less expensive and comprehensive. 相似文献
Sharp dynamic thermal gradient (∇T ≈ 45 °C mm−1) field‐driven assembly of cylinder‐forming block copolymer (c‐BCP) films filled with PS‐coated gold nanoparticles (AuNPs; dNP ≈ 3.6 nm, φNP ≈ 0–0.1) is studied. The influence of increasing AuNP loading fraction on dispersion and assembly of AuNPs within c‐BCP (PS‐PMMA) films is investigated via both static and dynamic thermal gradient fields. With φNP increasing, a sharp transition from vertical to random in‐plane horizontal cylinder orientation is observed due to enrichment of AuNPs at the substrate side and favorable interaction of PMMA chains with gold cores. Furthermore, a detachable capping elastomer layer can self‐align these random oriented PMMA microdomains into unidirectional hybrid AuNP/c‐BCP nanolines, quantified with an alignment order parameter, S.
Two new phenol based macroacyclic Schiff base ligands, 2,6-bis({N-[2-(phenylselenato)ethyl]}benzimidoyl)-4-methylphenol (bpebmpH, 1) and 2,6-bis({N-[3-(phenylselenato)propyl]}benzimidoyl)-4-methylphenol (bppbmpH, 2) of the Se2N2O type have been prepared by the condensation of 4-methyl-2,6-dibenzoylphenol (mdbpH) with the appropriate (for specific reactions) phenylselenato(alkyl)amine. These ligands with Cu(II) acetate monohydrate in a 2:1 molar ratio in methanol form complexes of the composition [(C6H2(O)(CH3){(C6H5)CN(CH2)nSe(C6H5)}{(C6H5)CO}2Cu] (3 (n = 2), 4 (n = 3)) with the loss of phenylselenato(alkyl)amine and acetic acid. In both these complexes, one arm of the ligand molecule undergoes hydrolysis, and links with Cu(II) in a bidentate (NO) fashion, as confirmed by single crystal X-ray crystallography of complex 3. The selenium atoms do not form part of the copper(II) distorted square planar coordination sphere which has a trans-CuN2O2 core. The average Cu–N and Cu–O distances are, respectively, 1.973(3) and 1.898(2) Å. The N–Cu–N and O–Cu–O angles are, respectively, 167.4(11)° and 164.5(12)°. The compounds 1–4 have been characterized by elemental analysis, conductivity measurements, mass spectrometry, IR, electronic, 1H and 77Se{1H} NMR spectroscopy and cyclic voltammetry. The interaction of complex 3 with calf thymus DNA has been investigated by a spectrophotometric method and cyclic voltammetry. 相似文献