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601 - 625 of 670
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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...
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The kinetics of oxidation of bis(1,4,7-triazacyclononane)nickel(II), [Ni(tacn)2]2+, by the peroxodisulphate anion has been studied in water as a function of S2O82- concentration and temperature. The reaction is first order in both the nickel(II) complex and S2O82-, with a second-order rate constant ...
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Nucleophilic substitution reactions with the cyclopentadienyliron (CpFe) complex of m- or p-dichlorobenzene with carbanion nucleophiles derived from ethyl acetoacetate (EAA), dibenzoylmethane (DBM) or diacetylmethane (DAM) were found to give only monosubstitution as previously observed for the CpFe ...
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Nucleophilic substitution reactions of the (η6-o-, -m-, or -p-chloronitrobenzene)(η5-cyclopentadienyl)iron cation (2a, 2b, or 2c, respectively) with aniline, n-butylamine, or pyrrolidine as nucleophile were investigated. It was found that only selective displacement of the nitro group occurred for...
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Pseudopterosins and pseudopteroxazole are intriguing marine natural products that possess notable antimicrobial activity with a commensurate lack of cytotoxicity. New semi-synthetic pseudopteroxazoles, pseudopteroquinoxalines and pseudopterosin congeners along with simple synthetic mimics of the ter...
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Reaction of η6-o-dichlorobenzene-η5-cyclopentadienyliron hexafluorophosphate (IPF6) with an excess of phenol or p-thiocresol in the presence of K2CO3 could give disubstitution of both chloro groups of I, while a similar reaction with one equivalent of the nucleophile, and under conditions of high ...
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Reactions of 5-norbornene-2-methanol with arene cyclopentadienyliron complexes led to the synthesis of two new classes of norbornene monomers with ether or ester bridges; ring-opening metathesis polymerization of these monomers using ruthenium-based catalysts gave rise to high molecular weight polym...
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Aluminum-based salen and salan complexes mediate the ring-opening polymerization (ROP) of rac-β-butyrolactone (β-BL), rac-lactide, and ε-caprolactone. Al-salen and Al-salan complexes exhibit excellent control over the ROP of rac-β-butyrolactone, yielding atactic poly(3-hydroxybutyrate) (PHB) wit...
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Edaravone, an electron spin trapper with radical scavenging activity, has been shown to be effective in reducing infarct volume in humans following ischemic stroke. However, concerns of edaravone-induced renal toxicity have limited its clinical adoption. Previous work has demonstrated that edaravone...
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Protein tyrosine phosphatases (PTPs) play an essential role in maintaining the proper tyrosine phosphorylation state of proteins. Abnormal tyrosine phosphorylation has been implicated in diseases as diverse as type 2 diabetes, cancer, immune disorders and neurological disorders, and thus inhibitors ...