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排序方式: 共有65条查询结果,搜索用时 218 毫秒
1.
本文用DSC方法研究了羟酸型含氟离聚体中不同金属离子种类、可离子化基团含量、配位结构单元构型及离子微区大小对离聚体中离子微区稳定性的影响。实验表明:离聚体中金属离子配位能力愈强,羟酸含量愈高,离子微区尺寸愈大,则相应离聚体中离子微区稳定性愈大。铅高聚体>锌离聚体>钙离聚体>钠离聚体。 相似文献
2.
The dinuclear copper(II) cryptate [Cu2L](ClO4)4 (1) cleaves the C-C bond of acetonitrile at room temperature to produce a cyanide bridged complex of [Cu2L(CN)](ClO4)3.2CH3CN.4H2O (2). The cleavage mechanism is presented on the basis of the results of the crystal structure of 2, electronic absorption spectra, ESI-MS spectroscopy, and GC spectra of 1, respectively. 相似文献
3.
Organolanthanide complexes of the type Cp'(2)LnCH(SiMe(3))(2) (Cp' = eta(5)-Me(5)C(5); Ln = La, Nd, Sm, Lu) and Me(2)SiCp' '(2)LnCH(SiMe(3))(2) (Cp' ' = eta(5)-Me(4)C(5); Ln = Nd, Sm, Lu) serve as efficient precatalysts for the regioselective intermolecular hydroamination of alkynes R'Ctbd1;CMe (R' = SiMe(3), C(6)H(5), Me), alkenes RCH=CH(2) (R = SiMe(3), CH(3)CH(2)CH(2)), butadiene, vinylarenes ArCH=CH(2) (Ar = phenyl, 4-methylbenzene, naphthyl, 4-fluorobenzene, 4-(trifluoromethyl)benzene, 4-methoxybenzene, 4-(dimethylamino)benzene, 4-(methylthio)benzene), di- and trivinylarenes, and methylenecyclopropanes with primary amines R' 'NH(2) (R' ' = n-propyl, n-butyl, isobutyl, phenyl, 4-methylphenyl, 4-(dimethylamino)phenyl) to yield the corresponding amines and imines. For R = SiMe(3), R = CH(2)=CH lanthanide-mediated intermolecular hydroamination regioselectively generates the anti-Markovnikov addition products (Me(3)SiCH(2)CH(2)NHR' ', (E)-CH(3)CH=CHCH(2)NHR' '). However, for R = CH(3)CH(2)CH(2), the Markovnikov addition product is observed (CH(3)CH(2)CH(2)CHNHR' 'CH(3)). For internal alkynes, it appears that these regioselective transformations occur under significant stereoelectronic control, and for R' = SiMe(3), rearrangement of the product enamines occurs via tautomerization to imines, followed by a 1,3-trimethylsilyl group shift to stable N-SiMe(3)-bonded CH(2)=CMeN(SiMe(3))R' ' structures. For vinylarenes, intermolecular hydroamination with n-propylamine affords the anti-Markovnikov addition product beta-phenylethylamine. In addition, hydroamination of divinylarenes provides a concise synthesis of tetrahydroisoquinoline structures via coupled intermolecular hydroamination/subsequent intramolecular cyclohydroamination sequences. Intermolecular hydroamination of methylenecyclopropane proceeds via highly regioselective exo-methylene C=C insertion into Ln-N bonds, followed by regioselective cyclopropane ring opening to afford the corresponding imine. For the Me(2)SiCp' '(2)Nd-catalyzed reaction of Me(3)SiCtbd1;CMe and H(2)NCH(2)CH(2)CH(2)CH(3), DeltaH() = 17.2 (1.1) kcal mol(-)(1) and DeltaS() = -25.9 (9.7) eu, while the reaction kinetics are zero-order in [amine] and first-order in both [catalyst] and [alkyne]. For the same substrate pair, catalytic turnover frequencies under identical conditions decrease in the order Me(2)SiCp' '(2)NdCH(SiMe(3))(2) > Me(2)SiCp' '(2)SmCH(SiMe(3))(2) > Me(2)SiCp' '(2)LuCH(SiMe(3))(2) > Cp'(2)SmCH(SiMe(3))(2), in accord with documented steric requirements for the insertion of olefinic functionalities into lanthanide-alkyl and -heteroatom sigma-bonds. Kinetic and mechanistic evidence argues that the turnover-limiting step is intermolecular C=C/Ctbd1;C bond insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. 相似文献
4.
Xie Ju Yang Yanwu Xi Ziqing Yang Zhenshan Zhang Xuecheng Ni Lubin 《Journal of inclusion phenomena and macrocyclic chemistry》2022,102(9-10):751-761
Journal of Inclusion Phenomena and Macrocyclic Chemistry - The combination of the electron donor and acceptor into a donor–acceptor system can transform the intermolecular charge transfer... 相似文献
5.
同核RELAY相干传递技术在复杂天然有机化合物1H谱解析中的应用 总被引:1,自引:0,他引:1
用同核化学位移相关谱和同核RELAY谱等二维NMR方法完全归属了复杂天然有机化合物人参皂甙Rb1的1H NMR谱线,并用积算符方法证实一级和二级RELAY实验中观察到的意外交叉峰是通过远程偶合传递的RELAY信号。 相似文献
6.
自然循环过冷沸腾流动不稳定性的实验研究 总被引:2,自引:0,他引:2
本文以氟里昂作工质,对自然循环过冷沸腾流动不稳定性进行了实验研究.实验过程中发现自然循环系统内可能发生高频脉动和低频脉动二种类型的过冷沸腾流动不稳定性.通过实验研究揭示了这二种类型流动不稳定性的发生机理,证实高频脉动属于声波型脉动,低频脉动属于密度波型脉动.通过实验得出了判断系统稳定性的界限,并使用积分方程无因次分析方法得出了预测密度波型流动不稳定性的经验公式. 相似文献
7.
Using the improved thermodynamic method, the acoustic non-linearity parameter B/A of binary biological mixtures — such as pig blood, sheep blood and bovine blood — is measured in order to test the mixture rules proposed by Apfel and Sehgal. The results show that the B/A values of the above-mentioned blood decrease with an increasing volume fraction of water. The B/A value varies linearly with the volume fraction of protein. It is also shown that, treated as a binary mixture, the blood obeys the trend that the B/A value varies with the volume of water. This is in agreement with the rules proposed by Apfel and Sehgal. However, the measured B/A value is not exactly equal to that of the mixture rules. 相似文献
8.
本文用定量处理2D NOE实验数据最精确的方法-全弛豫矩阵分析法定量分析了天然有机化合物显脉香茶菜素的相敏NOESY谱,计算出显脉香茶菜素分子中各质子间的交叉弛豫速率,根据1/rtf6∝σtf计算出相应的质子间距离,结果表明:用全弛豫矩阵分析法计算出的质子间距与分子力学计算以及用单晶X-射线衍射法测得的质子间距离基本一致,为用核磁共振方法确定分子在溶液中的三维空间结构提供了可靠的结构参数。 相似文献
9.
WANG Binghe DONG Yanwu TU Haiying WU Shengju SHANG Zhiyuan TONG Jie JIN Xiuchan WANG Ruie 《声学学报:英文版》1995,(3)
I.IntroductionForlongtime,itisoneofveryimportantquestionsinbiomcchanicscirc1estosetupady-namicsmode10fhumancardioscularsystemI'-'1.Peop1ehaveexpectedtostudythecomp1cxcardioscu1arsystemfromtheviewofthesy5temtheoryandtheinformati0ntheory.Wea1sopayattentiontothetheory0fTraditi0nalChinescMedicine(TCM)anditsc1inicalexperience.Thepulseisdrivenbytheheartandtransmittedbyb10odflowthrougharteries.ItgOesa1ongwayfarfromtheheart,andarrivesattheradia1artery.Thusitisaffectedbynoton1ythecon-ditionofthehe… 相似文献
10.
TONG Jie DONG Yanwu 《声学学报:英文版》1993,(4)
In this paper, several mixtrue rules of sound velocity and their useful ness in characterizing the components of biomedium are analysed. It is pointed out that for characterizing the components of biomedium, the rules are compatible with each other under certain conditions, and the errors between each rule and real sound velocity are diffferent. It concludes that there is no general rule suitable for various media among above mentioned rules. 相似文献