- Activation Volumes for Intramolecular Oxidative C-X (X = H, F, Cl or Br) Addition to Platinum(II) Imine Complexes as a Proof of the Intimate Mechanism
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The kinetics of C-X (X=H, F, Cl or Br) bond activation of ring-substituted, PhCHNCH2Ph, type imines via intramolecular oxidative addition to platinum(II) complexes has been studied in acetone and toluene solution at different temperatures and pressures.Although the activation parameters determined are within the range expected, the latter is extremely large (ΔH from 25 to 70 kJ mol-1, ΔS from -220 to -45 J K-1 mol-1, ΔV from -3.12 to -9.5 cm3 mol-1).No differences were found for the reactions carried out in acetone or toluene, indicating that no planar transition state is formed during the reaction and that a common highly ordered three-centered C-Pt-X intraction is present for all the imines used.A good correlation was also obtained for the ΔS and ΔV values, independently of the solvent used, confirming the non-polarity of the transition state.A deviation from this pattern is observed only for fluorinated imines both in acetone and toluene solutions; this result is interpreted by considering an earlier transition state for the oxidative addition of C-F that has not yet produced an important volume contraction of the platinum centre despite the important spacial organization of the ligand, as shown by the very negative values of ΔS.
- Crespo, Margarita,Martinez, Manuel,Pablo, Esther de
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p. 1231 - 1236
(2007/10/03)
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- 4-Nitro-2-trichloromethylphenylsulfenamides
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New 4-nitro-2-trichloromethylphenylsulfenamides having a fungicidal and bactericidal action, processes for their manufacture, fungicides containing these compounds as active ingredients, and a process for combating fungi with these compounds.
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- Thiolphosphoric acid-S-4-nitro-2-trichloromethylphenyl esters as fungicides
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New thiolphosphoric acid-S-4-nitro-2-trichloromethylphenyl esters of the formula STR1 where X denotes oxygen or sulfur, and R1 and R2 are identical or different and each denotes a substituted or unsubstituted aliphatic radical of 1 to 18 carbon atoms or a substituted or unsubstituted alicyclic radical of 5 to 18 carbon atoms, processes for their manufacture, fungicides containing these compounds as active ingredients, their manufacture, and processes for combating fungi with these novel compounds.
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- Polyhalobenzylic disulfooxonium compounds
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Polyhalobenzylic disulfooxonium compounds are produced by the reaction of aromatic methyl, halomethyl or hydroxymethyl substituents with sulfur trioxide. The disulfooxonium salts are readily converted to alcohols by hydrolysis to provide monomers for the production of fire resistant polymers and additives for polymers. Likewise, the disulfooxonium compounds of this invention present chemical intermediates for a wide range of useful products such as halogenated pesticides.
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- N-(fluorodichloromethylthio)-benzanilides
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New and valuable N-(fluorodichloromethylthio)-benzanilides, a process for their manufacture, fungicides containing these compounds as active ingredients, and a method of combatting fungi with these compounds.
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- Triazolylthiophosphoric acid esters
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Triazolylthiophosphonic esters corresponding to the formula SPC1 Wherein R1 represents a phenyl radical which is substituted by one or more fluorine, bromine and/or iodine atoms, by lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N groups, which may be the same or different, or by at least one chlorine and at least one fluorine, bromine or iodine atom, one lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N group, or represents an unsubstituted or halogenated and/or alkoxylated phenyl-lower alkyl radical or diphenylmethyl, and one of the symbols R2 and R3 represents hydrogen or a lower alkyl radical and the other represents the radical EQU1 wherein R4 represents a lower alkyl radical or the phenyl radical and R5 represents a lower alkyl radical their manufacture and their use in pest control.
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