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81.
82.
Summary A convenient synthesis of the ligand ethylenediaminetetraacetamide (L) is described, and a number of metal complexes of the general formula MLCln · xH2O (Mn+=CaII, MnII, FeII, CoII, NII, CuII, ZnII, MgII, BaII, CdII, HgII and LaIII) prepared. The deprotonated Cu(L-H)2 · 2 H2O complex has been characterised and the associated pK values determined. I.r., conductivity, magnetic susceptibility and electronic spectral data are discussed. 相似文献
83.
Graham LA Fout AR Kuehne KR White JL Mookherji B Marks FM Yap GP Zakharov LN Rheingold AL Rabinovich D 《Dalton transactions (Cambridge, England : 2003)》2005,(1):171-180
The manganese(I) tricarbonyl complexes (Bm(R))Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhBmMe)Mn(CO)3, the first bis(mercaptoimidazolyl)borate derivatives for this metal, have been readily prepared and fully characterized. In particular, the presence of three-center-two-electron Mn...H-B interactions in these species, both in solution and in the solid state, has been investigated using a combination of IR and NMR spectroscopies and, in the case of the methyl-, tert-butyl- and para-tolyl-substituted derivatives, by X-ray crystallography. To complement these synthetic and structural studies, the tris(mercaptoimidazolyl)borate complexes (TmMe)Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhTm(Me))Mn(CO)3, as well as the related pyrazolylbis(mercaptoimidazolyl)borate (pzBmMe)Mn(CO)3, have also been synthesized and characterized by a combination of analytical and spectroscopic techniques. 相似文献
84.
Nanoindentation with a Berkovich indenter is commonly used to investigate the mechanical behavior of small volumes of materials. To date, most investigators have made the simplifying assumption that the tip is spherical. In reality, indenter tips are much more complex. Here, we develop a new method to describe the tip shape using the experimentally determined area function of the indenter at small depths (0-100 nm). Our analysis accurately predicts the elastic load-displacement curve and allows the theoretical strength of a material to be determined from pop-in data. Application of our new method to single crystal Cr3Si shows that the predicted theoretical strengths are within 12% of the ideal strength G/2pi, where G is the shear modulus. 相似文献
85.
Rajendra J Baxendale M Dit Rap LG Rodger A 《Journal of the American Chemical Society》2004,126(36):11182-11188
Structures of carbon nanotube/ligand complexes were studied by flow linear dichroism (the differential absorption of light polarized parallel and perpendicular to the flow orientation direction) with the aim of establishing linear dichroism as a technique to study such systems. Anthracene, naphthalene, and DNA were chosen as ligands, and the potential for flow linear dichroism to probe ligands noncovalently (as well as covalently) bound to single-walled nanotubes is reported. Linear dichroism enables the determination of approximate orientations of the ligands on the carbon nanotubes. 相似文献
86.
Janka M He W Frontier AJ Eisenberg R 《Journal of the American Chemical Society》2004,126(22):6864-6865
The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BARF)2 having adjacent labile sites has been found to be a very effective catalyst for promoting the Nazarov cyclization of aryl vinyl and divinyl ketones. Spectroscopic evidence for a substate-catalyst complex before cyclization is presented. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via chelation. 相似文献
87.
Plieger PG Downard AJ Moubaraki B Murray KS Brooker S 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2157-2165
A bis(pyridine-armed) acyclic Schiff base ligand L1 has been synthesised from 3,6-diformylpyridazine and two equivalents of 2-(2-aminoethyl)pyridine. Reduction of this ligand using NaBH(4) resulted in the formation of the amine analogue L2. Complexes of the form [M(2)L1(mu-X)]Y(2)ClO(4)[where: M = Cu(II), X = OH(-) and Y = ClO(4)(-) 1, Cl(-) 2, Br(-) 3 or I(-) 4; M = Co(II), X = OH(-) and Y = ClO(4)(-) 5; M = Ni(II), X = SCN(-) 6 or X = N(3)(-) 7 and Y = ClO(4)(-)], and [Cu(2)L2(mu-OH)](ClO(4))(3) 8 were prepared and characterised. The complexes 1 and 5-7 have been characterised by single-crystal X-ray diffraction. The acyclic L1 ligand provides three nitrogen donor atoms per metal centre, including a pyridazine bridge between the metal centres, and the anion X also bridges the two metal centres. As required, coordinating solvent molecules or additional anions make up the remainder of the coordination sphere. The two copper centres of 1 are very strongly antiferromagnetically coupled (2J=-1146 cm(-1))via the pyridazine and hydroxide ion bridges, whereas the competing antiferromagnetic pyridazine bridging pathway and ferromagnetic 1,1-bridging azide pathway resulted in the observation of weak antiferromagnetic exchange in the dinickel(II) complex 7 (2J=-14 cm(-1)). Electrochemical examination of L1, L2 and complexes 1 and 5-8 revealed multiple redox processes. These have been tentatively assigned to a mixture of metal centred and ligand centred redox processes on the basis of cyclic voltammetry and coulometry results and comparisons with literature examples. 相似文献
88.
An evaluation of alpha-aryl-alpha-diazodiones in tandem carbonyl ylide formation-enantioselective [3 + 2]-cycloaddition reactions is described. Such substrates were designed to allow investigation of the electronic characteristics of the dipole upon asymmetric induction. Intramolecular cycloadditions (with a tethered alkene dipolarophile) were found to occur in good to quantitative yields, with a difference in ee exhibited by the two electronically different diazodiones 8 and 9. Intermolecular cycloadditions using diazodiones 12 and 13 with DMAD and arylacetylenes 16-18 again demonstrated that electronics play a key role in determining the outcome of the cycloaddition reactions. Enantioselectivities of up to 76% were observed. 相似文献
89.
Ashcroft AE 《Natural product reports》2003,20(2):202-215
Proteomics encompasses several disciplines in the quest to unravel the science of life. Mass spectrometry plays a key r?le in proteomics-associated analyses and this review describes that function in terms of the instrumentation used, the results generated, data interpretation and the advances in analytical techniques being made to deal with the production of highly specific, high throughput data. The review has 151 references. 相似文献
90.
Hervé G Hahn DU Hervé AC Goodworth KJ Hill AM Hailes HC 《Organic & biomolecular chemistry》2003,1(2):427-435
Methodologies to access water soluble large ringed calixarenes in good yield using efficient synthetic procedures have been investigated. Symmetrical partial functionalisations at the lower rim are described using activated [n]ethylene glycol chains and the addition behaviour contrasted with that of bromoalkanenitriles which proceeds with no observed regioselectivity. Full functionalisations of the calixarenes bearing hydrophilic groups are then investigated and a two-step procedure established which appears to be generally applicable for the addition of different [n]ethylene glycol chains. Furthermore, difunctionalisation under different reaction conditions are described. Throughout, strategies for the characterisation of these high mass compounds are outlined. 相似文献