35981-65-8Relevant academic research and scientific papers
The effect of chlorine and fluorine substitutions on tuning the ionization potential of benzoate-bridged paddlewheel diruthenium(II, II) complexes
Kosaka, Wataru,Itoh, Masahisa,Miyasaka, Hitoshi
, p. 8156 - 8168 (2015)
A series of paddlewheel diruthenium(II, II) complexes with various chlorine-substituted benzoate ligands (Cl-series) was synthesized as tetrahydrofuran (THF) adducts [Ru2(ClxPhCO2)4(THF)2]; where ClxPhCO2- = o-chlorobenzoate, o-Cl; m-chlorobenzoate, m-Cl; p-chlorobenzoate, p-Cl; 2,3-dichlorobenzoate, 2,3-Cl2; 2,4-dichlorobenzoate, 2,4-Cl2; 2,5-dichlorobenzoate, 2,5-Cl2; 2,6-dichlorobenzoate, 2,6-Cl2; 3,4-dichlorobenzoate, 3,4-Cl2; 3,5-dichlorobenzoate, 3,5-Cl2; 2,3,4-trichlorobenzoate, 2,3,4-Cl3; 2,3,5-trichlorobenzoate, 2,3,5-Cl3; 2,4,5-trichlorobenzoate, 2,4,5-Cl3; 3,4,5-trichlorobenzoate, 3,4,5-Cl3; 2,3,4,5-tetrachlorobenzoate, 2,3,4,5-Cl4. This Cl-series and the previously synthesized F-series together with four new fluorine-substituted derivatives, [Ru2(FxPhCO2)4(THF)2] (where FxPhCO2- = 2,3-difluorobenzoate, 2,3-F2; 2,4-difluorobenzoate, 2,4-F2; 2,5-difluorobenzoate, 2,5-F2; 2,3,5-trifluorobenzoate, 2,3,5-F3), were experimentally characterized with respect to solid-state structure, magnetic properties and electrochemistry. By tuning the substituents of the benzoate ligands using chlorine or fluorine atoms, the redox potential (E1/2) for [Ru2II,II]/[Ru2II,III]+ varied over a wide range of potentials from -40 mV to 360 mV (vs. Ag/Ag+ in THF). This was dependent on (i) the number of ortho-substituents, i.e. non-, mono- and di-o-substituted groups, with quasi-Hammett parameters for ortho-Cl and -F substitutions (σo = -0.272 and -0.217, respectively) and (ii) the general Hammett constants, σm and σp, for each group. The HOMO energy level calculated on the basis of the atomic coordinates of the solid-state structure was strongly affected by Cl- and F-substitutions as well as the redox potential in solution, which emphasizes the steric contribution of ortho-substituents in the energy level giving a deviation of EHOMO 0.3 eV and 0.55 eV for the Cl- and F-series, respectively.
Heterocyclic pesticidal compounds
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, (2008/06/13)
Compounds of the formula (I) STR1 which contain between 10 and 27 carbon atoms, and wherein m and n are independently selected from 0, 1 and 2; R2a is hydrogen, methyl, or ethyl; R2b is acetylene or contains between 3 and 18 carbon atoms and is a group R7, wherein R7 is a C1-13 non-aromatic hydrocarbyl group, optionally substituted by a cyano or C1-4 carbalkoxy group and/or by one or two hydroxy groups and/or by one to five halo atoms which are the same or different and/or by one to three groups R8 which are the same or different and each contain one to four hetero atoms, which are the same or different and are chosen from oxygen, sulphur, nitrogen and silicon, 1 to 10 carbon atoms and optionally 1 to 6 fluoro or chloro atoms or R2b is a 6-membered aromatic ring substituted by cyano and/or by one to three groups R8 and/or by a group --C CH, --C C-R7 or C C-halo and/or by one to five halo atoms and/or by one to three C1-4 haloalkyl groups wherein R7 and R8 are as hereinbefore defined; R4 and R6 are the same or different and are chosen from hydrogen, methyl, trifluoromethyl or cyano; and R5 is hydrogen or methyl provided that R2b is not propyl or butyl are described which have pesticidal activity, particularly against arthropod pests. Pesticidal formulations containing the compounds of the formula (I), their use in the control of pests and method for their preparation are also disclosed.
