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Acceptor Substituents (acceptor + substituent)

Distribution by Scientific Domains
Chemistry75%

Selected Abstracts

First Propargyl Azides Bearing Strong Acceptor Substituents and Their Effective Conversion into Allenyl Azides: Influence of the Electronic Effects of Substituents on the Reactivity of Propargyl Azides,,

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2005
Joseph Rodolph Fotsing
Abstract We have succeeded in the synthesis of propargyl azides containing 1- or 3-phenylthio functionalities. The selective oxidation of their sulfur atoms to sulfoxides and sulfones allows access to the first propargyl azides bearing acceptor substituents. Interestingly, the prototropic rearrangement of the latter propargyl azides leads to the formation of allenyl azides with relatively high stabilities and with moderate to good yields. Propargyl azides containing phenylthio functionalities react in the presence of nucleophiles to afford the expected N -unsubstituted 1,2,3-triazoles via short-lived allenyl azides. These results are entirely different from those of the corresponding sulfoxides and sulfones, which react under the analogous conditions either to produce the corresponding bis(triazolo)pyrazine derivatives or to yield newly substituted vinyl azides. The latter compounds can successfully be used as starting material providing access to azirines. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Syntheses, Structures and Theoretical Investigations of 1,4,3,4,5,4 -Trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2003
Carsten Knapp
Abstract The syntheses of the title compounds RCN5S3 with electron-withdrawing aryl substituents [R = 2-FC6H4 (1m), 4-FC6H4 (1n), 2,6-F2C6H3 (1o), C6F5 (1p), 4-NCC6H4 (1q) and Cl3C (1r)] are described. The X-ray structures of 1n, 1o, 1q and 1r, together with those of Me2NCN5S3 (1b) and 4-CH3C6H4CN5S3 (1f), are reported. The experimentally determined dependence of the bond lengths on the substituents R within the bicyclic system RCN5S3 is well-reflected in the results of the theoretical calculations (RHF, MP2, B3LYP). The bonding model developed shows that acceptor substituents do not influence bonding within the bicycle. In the solid state, two fundamentally different primary interactions of the RCN5S3 molecules are observed; "stacking" and "dimerisation", which can be rationalised by electrostatic interactions between the CN5S3 units. However, secondary effects , the interactions between the R substituents , may be even more dominant. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

First Propargyl Azides Bearing Strong Acceptor Substituents and Their Effective Conversion into Allenyl Azides: Influence of the Electronic Effects of Substituents on the Reactivity of Propargyl Azides,,

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2005
Joseph Rodolph Fotsing
Abstract We have succeeded in the synthesis of propargyl azides containing 1- or 3-phenylthio functionalities. The selective oxidation of their sulfur atoms to sulfoxides and sulfones allows access to the first propargyl azides bearing acceptor substituents. Interestingly, the prototropic rearrangement of the latter propargyl azides leads to the formation of allenyl azides with relatively high stabilities and with moderate to good yields. Propargyl azides containing phenylthio functionalities react in the presence of nucleophiles to afford the expected N -unsubstituted 1,2,3-triazoles via short-lived allenyl azides. These results are entirely different from those of the corresponding sulfoxides and sulfones, which react under the analogous conditions either to produce the corresponding bis(triazolo)pyrazine derivatives or to yield newly substituted vinyl azides. The latter compounds can successfully be used as starting material providing access to azirines. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Electronic Structure of Self-Assembled Monolayers on Au(111) Surfaces: The Impact of Backbone Polarizability

ADVANCED FUNCTIONAL MATERIALS, Issue 23 2009
LinJun Wang
Abstract Modifying metal electrodes with self-assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density-functional-theory study on a series of organic thiols self-assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi-level pinning is observed. Nevertheless, independent of the backbone, polar head-group substitutions have no effect on the level alignment. For the work-function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work-function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure,property relationships needed for the future development of functional organic interfaces. [source]