ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • kinetics  (17)
  • supramolecular chemistry  (17)
  • 1
    ISSN: 0947-6539
    Keywords: calixarenes ; cavitands ; molecular modeling ; resorcinarenes ; supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coupling reactions of calix[4]arenes and modified resorcin[4]arenes have been investigated. Reaction of mono(chloroacetamido)calix[4]arene 4 with tetrahydroxycavitand 9 gave the 1:1 coupled product 13 in 61% yield. Combination of upper-rim 1,3-difunctionalized calix[4]arene 5 with 9 afforded predominantly the 2:1 calix-resorcinarene 18 in 47% yield. Reaction of 1,2-difunctionalized calix[4]arene 6 with 9 gave five products, namely, endo 1:1 (19), exo 1:1 (20), endo-endo 2:1 (21), endo-exo 2:1 (22), and exo-exo 2:1 (23) in ratios that depend on the reaction conditions. The stereochemistry of the different products was determined with NOESY experiments. The structures of 21 a and 23 b were calculated by using molecular mechanics, which revealed that intramolecular hydrogen bonds are only present in the former. Reaction of 1,2-bis(chloroacetamido)calix[4]arene 26, which has two additional nitro groups at the remaining aromatic rings, with 9 yielded three different products, namely, endo 1:1 (28), endo-endo 2:1 (30), and endo-exo 2:1 (32) in ratios that depend on the reaction conditions. There is a preference for the endo orientation in the formation of the 1:1 coupled product, probably owing to an interaction of the nitro groups with the cavitand in the transition state. After conversion of the nitro groups in 28 into chloroacetamido moieties, reaction with Cs2CO3 in DMF under high-dilution conditions afforded holand 33 in 26% yield together with calix[4]arene-based carceplex 34 with an encapsulated DMF molecule (27% yield). Holand 33 was obtained in 33% yield by reaction of the tetrakis(chloroacetamide) endo-endo 2:1 isomer 31 with tetrahydroxycavitand 9. Holand 33 contains a cavity of nanosize dimensions. Molecular mechanics simulations indicate that holand 33 adopts a conformation with eight hydrogen bonds and a large, preorganized cavity with two entrances of smaller dimensions. Molecular dynamics simulations of holand 33 in both CHCl3 and THF showed that four solvent molecules can be accommodated in the cavity at well-defined positions.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    ISSN: 0947-6539
    Keywords: carbonyl complexes ; cobalt compounds ; kinetics ; mechanistic studies ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substitution reaction of [Co(CO)4]- by P(OPh)3 was investigated in THF. Under a CO atmosphere, the reaction consists of an equilibrium, which, in order to be established, needs [Co2(CO)6(P(OPh)3)2]. The catalysis by this neutral carbonyl is formally related to a previously reported case, where either [Co2(CO)8] or [Co4(CO)12] was found to be necessary for the 13CO scrambling in [Co(CO)4]-. The kinetic analysis reported in this paper indicates, however, that the two CO labilizations differ in their mechanism-the substitution by P(OPh)3 is ascribed to a disproportionation-synproportionation of [Co2(CO)6(P(OPh)3)2].
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    ISSN: 0947-6539
    Keywords: anthraquinones ; molecular devices ; supramolecular chemistry ; titanium dioxide ; viologens ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linked viologen-anthraquinone molecules are attached to TiO2 nanocrystallites supported on a conducting glass substrate. The resulting assembly is incorporated as the working electrode in an electrochemical cell. Under opencircuit conditions, band-gap excitation of the semiconductor nanocrystallite results in viologen-mediated electron transfer to anthraquinone. Prior application of a negative potential step, which results in 2e-/2H+ reduction of anthraquinone, permits electron transfer only to viologen. At positive applied potentials, electron transfer following band-gap excitation is largely suppressed. Some implications of these findings for modulation of function in molecular devices are considered.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    ISSN: 0947-6539
    Keywords: chirality ; coordination modes ; macrocyclic ligands ; octahedral complexes ; supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    ISSN: 0947-6539
    Keywords: amine boranes ; carbocations ; kinetics ; linear free enthalpy relationship ; reductions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of trialkylamine boranes and pyridine boranes with benzhydryl cations have been determined photometrically. Second-order rate laws are obeyed, first-order with respect to amine borane concentration and first-order with respect to carbocation concentration. As for other reactions of carbocations with neutral nucleophiles, the rates of these reactions are only slightly affected by solvent polarity. The structure - reactivity relationships and kinetic isotope effects are in accord with a polar mechanism proceeding through a transition state where the migrating hydride is partly bound to the entering carbon and to the leaving boron atom. The rate constants correlate linearly with the electrophilicity parameters E of the carbenium ions. It is therefore possible to use the linear free enthalpy relationship logk2 = s(E+N) for determining nucleophilicity parameters N for the amine boranes and to compare their hydride-donating abilities with those of other non-charged hydride donors (silanes, germanes, stannanes, and dihydropyridines).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    ISSN: 0947-6539
    Keywords: alkali metals ; catechol ligands ; NMR spectroscopy ; supramolecular chemistry ; titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spontaneous self-assembly of methylene-bridged dinuclear TiIV complexes M4[L3Ti2] (L = 1-3) from CH2-bridged di(catechol) ligands (1-H4-3-H4) was found to proceed in the presence of lithium or sodium carbonate acting as a base (M = Li, Na). In contrast, only an unspecific mixture of coordination compounds was obtained in the presence of potassium carbonate. This difference in behavior is due to the ability of Li+ or Na+ to stabilize the triple-stranded dinuclear titanium(IV) species [L3Ti2]4-. In the solid state, Li4[(1)3Ti2] exhibits a highly symmetric structure with three lithium cations bound to the meso-helicate tetraanion. 6Li NMR together with 1H NMR studies at variable temperature revealed that, in solution, an unsymmetrical „bowl-shaped“ species is formed with only two Li+ bound to the anion. A methyl substituent on the methylene spacer of the di(catechol) ligand (ligand 2) led to supramolecular systems with new stereocenters and thus a higher content of information. However, only one of the four possible diastereoisomeric metal complexes of [(2)3Ti2]4- was observed. A third type of ligand, with a methyl group attached to one terminus of the linear ligand, was also investigated. The synthesis of such an unsymmetrical ligand, 3-H4, was readily achieved starting from 2,3-dimethoxyben-zyl alcohol (4) and 2,3-dimethoxybenz-aldehyde (6). Upon complexation, the ligand 3-H4 led to a statistical mixture of the two possible isomers of the dinuclear titanium(IV) complex [(3)3Ti2]4-.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    ISSN: 0947-6539
    Keywords: antitumour agents ; DNA ; kinetics ; nucleotides ; platinum complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the first direct comparison of the kinetics of platination of defined single- and double-stranded DNA with the anticancer drug cisplatin. The courses of the reactions of the 14-mer duplex d(A-T-A-C-A-T-G-G-T-A-C-A-T-A)·d(T-A-T-G-T-A-C-C-A-T-G-T-A-T) with [15N]cisplatin and cis-[PtCl(H2O)-(15NH3)2]+ and of each of the single strands with [15N]cisplatin have been studied at 298 K, pH 6, by [1H, 15N] NMR spectroscopy. As expected the reactions of cisplatin proceed via cis-[PtCl(H2O)(NH3)2]+, and lead to two monofunctional adducts on the duplex and two on the GG single strand. In both the GG single strand and the duplex, one of the two G's is platinated faster than the other (by a factor of ca. 4). Remarkably, ring closure on the duplex to form the GG chelate occurs about an order of magnitude faster for one monofunctional adduct than for the other. The latter monofunctional adduct has distinctive 1H and 15N NMR chemical shifts for Pt-NH3, and is very long-lived (persists for 〉5 d). The Pt-Cl bond in this monofunctional adduct is protected from hydrolysis by the duplex. In contrast, the two monofunctional adducts on the GG single strand undergo ring closure at about the same rate. Equilibria between kinked and distorted forms of the GG platinated duplex, the platination of G's on the complementary strand, and the potential biological significance of long-lived monofunctional adducts of platinum drugs with DNA are discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    ISSN: 0947-6539
    Keywords: complexes with nitrogen ligands ; ruthenium complexes ; self-assembly ; supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of mono- and dimetallic complexes of rack type containing a dinucleating bis-tridentate ligand and RuII-2,2′:6′,2′-terpyridyl (tpy) sites were synthesised and characterised. The 1H NMR spectra of the dimetallic complexes were correlated to structural features, and the crystal structures of the dimetallic complexes were determined. They provide information about the way in which the central substitutent affects the overall shape of the racks and the relative disposition of the metal centres, measured by the pinching angle of the bis-tridentate ligand and the convergence angle of the ancillary tpy units. The latter demonstrates that a CH3 group yields the least bent complex and indicates how parallel the tpy units are. The dimetallic racks exhibit metal-metal interactions mediated by the bis-tridentate ligands as indicated by electrochemical and spectroscopic methods. The bridging-ligand π* orbital and the dπ metal orbital are stabilised by complexation of a second metal. The results obtained provide guidelines for the design of extended racks bearing several metal centres in a linear arrangement, which also represent potential components of molecular electronic devices.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    ISSN: 0947-6539
    Keywords: bipyridine ligands ; helicates ; kinetics ; mass spectrometry ; self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The self-assembly of the pentanuclear double helicates Hh, Ha and He from the corresponding oligobipyridine strands Lh, La and Le and Cu1 ions has been investigated by NMR and electrospray mass spectrometry (ESMS). Where as Hh is assembled rapidly (in less than 20 min), He (about 20 h) and especially Ha (about 60 h) form much more slowly. The rate decreases strongly with increasing steric bulk of the substituents in the 4,4′-positions on the bipyridine units; this indicates that the search processes (wrapping, unwrapping) that lead to the final helicate are strongly hindered by the size of the substituents. The ESMS data give information about the species present in solution under different conditions and allow the formulation of possible formation pathways, which may involve, in particular, helicates of hairpin type.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    ISSN: 0947-6539
    Keywords: macrocycles ; rotaxanes ; sulfon-amides ; supramolecular chemistry ; template synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparative syntheses of new nano-sized rotaxane assemblies are described, namely, of the first tris[2]rotaxane, 15, the first bis[2]rotaxane connected at the axles, 4, and the first [3]rotaxane with two different axles, 12 (unsymmetrical “bis[2]rotaxane”). These syntheses were made possible by the directed incorporation of a sulfonamide group into the amide-linked rotaxane building blocks. The sulfonamide moiety can be used as a functional group in alkylation reactions, allowing the further attachment of building blocks in good yields. The successful synthesis of these new rotaxane architectures demonstrates the synthetic potential of this sulfonamide strategy in the preparation of multirotaxane and dendritic rotaxane structures.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...