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The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to pho...
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The ketene derived from diazoquinone 5 can be readily detected by laser photolysis techniques with IR detection and its behavior agrees with that observed with more conventional UV-visible detection. The ketene reacts with amines (e.g. k similar to 7 x 10(7) M-1 s(-1) for diethylamine) to give ylide...
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The stereochemistry of 1,2-H migration in ethylchlorocarbene (1) and chloromethylchlorocarbene (2) has been studied by ab initio methods. Geometries of the ground and transition states of a conformational equilibrium and the 1,2 rearrangement were optimized at the DFT (B3LYP) and MP2 levels of theor...
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The kinetics of oxidation of 1,4,8,11-tetraazacyclotetradecane-5,7-diamidonickel(II) ('nickel dioxocyclam') by peroxodisulfate have been measured in a range of binary aqueous solvent mixtures. Reaction rates are retarded by the presence of organic co-solvents, indicative of destabilization of the tr...
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The first direct determination of a 1,2-chlorine atom shift in a chlorobenzylcarbene was achieved by nanosecond laser flash photolysis. Arrhenius activation parameters of E(act) = 3.39 +/- 0.14 kcal mol-1 and log [A(s-1)] = 10.98 +/- 0.14 were obtained for 1,2-chlorine migration in alpha-methyl-alph...
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Oxidation of Cr[N(SiMe3)(2)](2)(THF)(2) with iodine and dicumyl peroxide results in tetrahedral Cr(IV)Cr[N(SiMe3)(2)](2)I-2 and trigonal planar Cr(III) Cr[N(SiMe3)(2)](OCMe2Ph)(2), respectively; both complexes have been characterised by single-crystal X-ray diffraction, and both are active for ethyl...
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1,10-Dichlorodecane (D2C10) is shown to be effectively photodegraded in aqueous suspensions of TiO2 using a photoreactor equipped with 300 nm lamps. Solutions exposed to UV light intensities of 3.6 × 10-5 Ein L-1 min-1, established by ferrioxalate actinometry, showed negligible direct photolysis in...
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Nanosecond laser flash photolysis (lambda = 355 nm) of an aqueous solution of 3-chloro-3-p-chlorophenyldiazirine in isooctane produces a transient absorption at 310 nm due to the formation of the carbene: In the presence of 2-vinylpyridine, a second transient with a broad absorption band peaking at ...
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The kinetics of oxidation of several nickel(II) tetraazamacrocycles by the peroxydisulphate anion have been studied in water and in binary aqueous mixtures. The reactions proceed via an ion-pairing pre-equilibrium, followed by metal ion-assisted peroxy-bond fissure within the ion-pair solvent shell ...
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The synthesis of an aromatic ether complex of cyclopentadienyliron containing two terminal aldehyde groups was achieved via metal-mediated nucleophilic aromatic substitution reactions. This dialdehyde monomer was subsequently reacted with a variety of aliphatic and aromatic diamines to produce the c...
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The dissociative step of a dissociative, or D, substitution mechanism exhibits a volume of activation, V1, which is independent of the nature of the incoming nucleophile. For the reaction of [Fe(CN)5(3,5Me2-py)]3?(3,5Me2-py = 3,5-d...
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The synthesis and characterization of a new class of bis(cyclopentadieny1iron) arene complexes of disulfides and diamines with aliphatic and aromatic bridges are presented. Reactions of the aromatic or aliphatic dithiols with a wide range of cyclopentadienyliron complexes of chloroarenes (la-i), in ...
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The rate constant for the reaction of benzylchlorocarbene with HCl is 4.7 x 10(9) dm3 mol-1 s-1.
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Bryostatin 1, a natural product anticancer agent isolated from a marine bryozoan, has been shown in tissue culture to activate protein kinase C. This agent has recently undergone Phase I testing in humans given either as a bolus i.v. injection or a continuous infusion. To understand how bryostatin 1...