首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   63篇
  免费   2篇
化学   59篇
数学   3篇
物理学   3篇
  2020年   1篇
  2019年   1篇
  2018年   4篇
  2016年   2篇
  2015年   3篇
  2011年   2篇
  2010年   1篇
  2009年   1篇
  2008年   1篇
  2007年   3篇
  2006年   2篇
  2005年   6篇
  2004年   6篇
  2003年   6篇
  2002年   8篇
  1999年   2篇
  1997年   3篇
  1996年   3篇
  1993年   1篇
  1992年   3篇
  1991年   1篇
  1989年   1篇
  1988年   2篇
  1985年   1篇
  1976年   1篇
排序方式: 共有65条查询结果,搜索用时 15 毫秒
1.
A new tripodal ligand, tris[2-(((2-thiazolyl)methylidene)amino)ethyl]amine (Tatren), has been synthesized and characterized by NMR, IR, and UV-visible absorbance spectroscopy and elemental analysis. Tatren forms stable complexes with transition metal ions (Zn(2+), 1; Mn(2+), 2; Co(2+), 3) and the alkaline earth metal ions (Ca(2+), 4; Mg(2+), 5). Single-crystal X-ray structures of 1, 2, and 5 revealed six-coordinate chelate complexes with formula [M(Tatren)](ClO(4))(2) in which the metal centers are coordinated by three thiazolyl N atoms and three acyclic imine N atoms. Crystals of 1, 2, and 5 are monoclinic, P2(1)/c space group. Crystals of 4 are triclinic, P space group. The Ca(2+) complex is eight-coordinate with all N atoms of Tatren and one water molecule coordinated to the metal ion. Spectrophotometric titrations show that formation constants for the chelates of metal ions are >1 in methanol. Free Tatren inhibits the catalytic domain of matrix metalloproteinase-13 (MMP-13, collagenase-3) with K(i) = 3.5 +/- 0.6 microM. Molecular mechanics-based docking calculations suggest that one leg of Tatren coordinates to the catalytic Zn(2+) in MMPs-2, -9, and -13 with significant hydrogen bonding to backbone amide groups. High-level DFT calculations suggest that, in the absence of nonbonded interactions between Tatren and the enzyme, the most stable first coordination sphere of the catalytic Zn(2+) is achieved with three imidazolyl groups from His residues and two imine N atoms from one leg of Tatren. While complexes (1-3) do not inhibit MMP-13 to a significant extent, 4 does (K(i) = 30 +/- 10 microM). Hence, this study shows that tripodal chelating ligands of this class and their Ca(2+) complexes have potential as active-site inhibitors for MMPs.  相似文献   
2.
3.
To understand the coordination chemistry of zinc-binding groups (ZBGs) with catalytic zinc centers in matrix metalloproteinases (MMPs) and disintegrin metalloproteases (ADAMs), we have undertaken a model compound study centered around tris(3,5-methylphenypyrazolyl)hydroboratozinc(II) hydroxide and aqua complexes ([Tp(Ph,Me)ZnOH] and [Tp(Ph,Me)Zn(OH2)]+, respectively, wherein (Tp(Ph,Me))- = hydrotris(3,5-methylphenylpyrazolyl)borate) and the products of their reactions with a class of chelating Schiff's base ligands. The results show that the protic ligands, HL (HL = N-propyl-1-(5-methyl-2-imidazolyl)methanimine (5-Me-4-ImHPr), N-propyl-1-(4-imidazolyl)methanimine (4-ImHPr), and N-propyl-1-(2-imidazolyl)methanimine (2-ImHPr)), react with [Tp(Ph,Me)ZnOH] and give products with the general formula [Tp(Ph,Me)ZnL], whereas reactions with neutral aprotic ligands, L' (L' = N-propyl-1-(1-methyl-2-imidazolyl)methanimine (1-Me-2-ImPr) and N-propyl-1-(2-thiazolyl)methanimine (2-TaPr)), yield the corresponding [Tp(Ph,Me)ZnL]+ complexes. Although the phenol group of N-propyl-1-(2-hydroxyphenyl)methanimine (2-HOPhPr) is protic, this ligand forms a cationic four-coordinate complex containing an intraligand hydrogen bond. The solid-state structures of these complexes were determined by single-crystal X-ray diffraction, and the results showed that the protic ligands form five-membered chelates of the Zn2+ ion. All ligands displace the aqua ligand in [Tp(Ph,Me)Zn(OH2)]+ to yield complexes having 1H NMR spectra consistent with the formation of five membered chelates. The 1H resonance frequencies of the chelating ligands typically shift upfield upon coordination to the zinc center, due to ring current effects from the pendant phenyl groups of the (Tp(Ph,Me))- ligand. Thus, the 1H NMR spectra provide a convenient and sensitive means of tracking the solution reactions by titration. The resulting series of spectra showed that the stabilities of the chelates in solution depend on the propensity of the ligands to deprotonate upon chelation of the zinc center. The behaviors of these bidentate ZBGs provide insight into the structural and electronic factors that contribute to the stabilities of inhibited MMPs and ADAMs and suggest that the proton acidity of the coordinated ZBG may be a crucial criterion for inhibitor design.  相似文献   
4.
A series of new platinum(II) and platinum(IV) complexes of the type [PtII(HMI)2X] (where HMI=hexamethyleneimine, X=dichloro, sulfato, 1,1-cyclobutanedicarboxylato [CBDCA], oxalato, methylmalonato, or tatronato) and [PtIV(HMI)2Y2Cl2] (where Y=hydroxo, acetato, or chloro) were synthesized and characterized by infrared (IR) spectroscopy, 13C and 195Pt nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Among the complexes synthesized, [PtII(hexamethyleneimine)2(1,1-cyclobutanedicarboxylato)]·H2O was examined by single-crystal X-ray diffraction. The slightly distorted square planar coordination environment of the platinum metal includes the amino group of the hexamethyleneimine (HMI) molecule and the oxygen atoms of the carboxylato ligand. The cyclobutanedicarboxylic acid (CBDCA) molecule adopts six-member chelating rings with platinum. Hydrogen bonding plays an important part in holding the crystal lattice together.  相似文献   
5.
Recent years have seen dramatic growth in our understanding of the biological roles of nitric oxide (NO). Yet, the fundamental underpinnings of its reactivities with transition metal centers in proteins and enzymes, the stabilities of their structures, and the relationships between structure and reactivity remains, to a significant extent, elusive. This is especially true for the so-called ferric heme nitrosyls ([FeNO](6) in the Enemark-Feltham scheme). The Fe-CO and C-O bond strengths in the isoelectronic ferrous carbonyl complexes are widely recognized to be inversely correlated and sensitive to structural, environmental, and electronic factors. On the other hand, the Fe-NO and N-O bonds in [FeNO](6) heme complexes exhibit seemingly inconsistent behavior in response to varying structure and environment. This report contains resonance Raman and density functional theory results that suggest a new model for FeNO bonding in five-coordinate [FeNO](6) complexes. On the basis of resonance Raman and FTIR data, a direct correlation between the nu(Fe)(-)(NO) and nu(N)(-)(O) frequencies of [Fe(OEP)NO](ClO(4)) and [Fe(OEP)NO](ClO(4)).CHCl(3) (two crystal forms of the same complex) has been established. Density functional theory calculations show that the relationship between Fe-NO and N-O bond strengths is responsive to FeNO electron density in three molecular orbitals. The highest energy orbital of the three is sigma-antibonding with respect to the entire FeNO unit. The other two comprise a lower-energy, degenerate, or nearly degenerate pair that is pi-bonding with respect to Fe-NO and pi-antibonding with respect to N-O. The relative sensitivities of the electron density distributions in these orbitals are shown to be consistent with all published indicators of Fe-N-O bond strengths and angles, including the examples reported here.  相似文献   
6.
7.
The stereochemistry of lead(II) complexes with S- and Se-donor atom ligands, including mixed ligand complexes is reviewed with respect to the geometry of the first coordination sphere of the Pb(II) atom in these compounds and rationalized in terms of the valence shell electron-pair repulsion (VSEPR) model. The most comprehensively structurally characterized classes of lead(II) thio and seleno complexes are discussed, including monothio-, dithio(seleno)-, trithio- and tetrathio-complexes, as well as Pb(II) dialkyldithio(seleno)carbamates, alkylxanthates and dialkyl(aryl) phosphorodithio(seleno)lates. Data about the polyhedral shape of the primary coordination sphere, coordination number (CN), bond lengths (primary and secondary) and bond angles of the Pb(II) atom in the compounds under investigation are systematized in comprehensive tables. The particularities of the stereochemistry of Pb(II) complexes with S(Se)-donor atom ligands are comparatively discussed with the stereochemistry of lead(II) complexes with oxygen donor ligands.  相似文献   
8.
9.
Iron and manganese complexes with derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine (bispicen) have previously been found to be efficient catalysts for hydrocarbon oxygenation. Methylation can potentially impact the conformation of the ligand around the metal center and the electronic character of the bound metal ion; each of these, in turn, impacts reactivity. Reported are mononuclear manganese(II) and iron(II) compounds with bispicen and five increasingly methylated derivatives. The extent and sites of methylation strongly impact the optical and electrochemical properties of the manganese and iron complexes. Increased methylation is correlated with more positive M(III/II) reduction potentials. Structural analysis of the Mn(II) series reveals two ligand conformations that have never been observed for the bispicen framework, cis-β and trans, in addition to the common cis-α conformation. (1)H NMR spectra of the structurally characterized iron compounds are consistent with mixtures of these conformers, suggesting that bispicen coordination is both more flexible and more dynamic than previously thought.  相似文献   
10.
The title complexes, hexaaquacobalt(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Co(H2O)6][Bi2(C7H4NO4)4]·2H2O, (I), and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Ni(H2O)6][Bi2(C7H4NO4)4]·2H2O, (II), are isomorphous and crystallize in the triclinic space group P. The transition metal ions are located on the inversion centre and adopt slightly distorted MO6 (M = Co or Ni) octahedral geometries. Two [Bi(pydc)2] units (pydc is pyridine‐2,6‐dicarboxylate) are linked via bridging carboxylate groups into centrosymmetric [Bi2(pydc)4]2− dianions. The crystal packing reveals that the [M(H2O)6]2+ cations, [Bi2(pydc)4]2− anions and solvent water molecules form multiple hydrogen bonds to generate a supramolecular three‐dimensional network. The formation of secondary Bi...O bonds between adjacent [Bi2(pydc)4]2− dimers provides an additional supramolecular synthon that directs and facilitates the crystal packing of both (I) and (II).  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号