Stereochemistry of oxidative addition of methyl iodide and hydrogen peroxide to organoplatinum(II) complexes having an appended phenol group and the supramolecular chemistry of the platinum(IV) products

n-Octadecyl S-methyl xanthate, m.p. 38–39°, and n-hexadecyl S-methyl xanthate, m.p. 28–28.5°, were prepared for the first time, and were used to study the behavior of the S-methyl xanthate group toward reagents commonly used in research on carbohydrates. Although stable to some conditions of acetylation, hydrolysis, and methanolysis, the S-methyl xanthate group was destroyed by all methylating agents tried, with the exception of nitrosomethylurethane. The latter reagent converted a sodium xanthate salt in high yield to the S-methyl ester. Octadecyl and hexadecyl S-methyl xanthates when oxidized with hydrogen peroxide yielded crystalline substances of composition C20H40O4S2 and C18H36O4S2, respectively, whose structures were not determined. These substances each contained three additional oxygen atoms. Various attempts to estimate the S-methyl xanthate group by oxidation with bromine or periodic acid, or by reduction to methyl iodide, were unsuccessful.

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Oxidative addition chemistry of dimethyl(dipyridyl ketone)platinum(II)

Canadian Journal of Chemistry ◽

10.1139/v05-028 ◽

2005 ◽

Vol 83 (6-7) ◽

pp. 595-605 ◽

Cited By ~ 36

Author(s):

Fenbao Zhang ◽

Michael E Broczkowski ◽

Michael C Jennings ◽

Richard J Puddephatt

Keyword(s):

Hydrogen Peroxide ◽

Key Words ◽

Acetyl Chloride ◽

Oxidative Addition ◽

Protonated Form ◽

Supramolecular Polymer ◽

Hydrolysis Of ◽

Mecn Solution ◽

Dipyridyl Ketone ◽

Methyl Triflate

The dimethylplatinum(II) complex [PtMe2(DPK)] (DPK = di-2-pyridyl ketone) undergoes easy oxidative addition to give platinum(IV) complexes. For example, reaction of [PtMe2(DPK)] with MeI gave [PtIMe3(DPK)], reaction with N-chlorosuccinimide in methanol gave [PtCl(OMe)Me2(DPK)], and reaction with [FN(CH2CH2)2NCH2Cl][BF4]2 in MeCN gave [PtF(NCMe)Me2(DPK)][BF4]. In several cases, the ketone group of the DPK ligand took part in the reactions. For example, oxidation of [PtMe2(DPK)] by air or hydrogen peroxide gave [Pt(OH)Me2(DPKOH)] (DPKOH = κ3-NN′O-(2-C5H4N)2C(OH)O), which reacted with HCl to give [PtClMe2(DPKOH)] or with excess acetyl chloride to give [PtCl2Me2(DPK)]. Reaction of [PtMe2(DPK)] with methyl triflate in MeCN solution gave [PtMe3(NCMe)(DPK)][OTf], which reacted with more MeOTf in the presence of base to give [PtMe3{DPC(OMe)2}][OTf], where DPC(OMe)2 = κ3-NN′O-(2-C5H4N)2C(OMe)2. Hydrolysis of [PtF(NCMe)Me2(DPK)][BF4] gave [Pt{NHC(=O)Me}Me2(DPKOH)], which crystallized in partially protonated form as an unusual supramolecular polymer [Pt{NHC(=O)Me}Me2(DPKOH)]·0.5HBF4.Key words: platinum, oxidative addition, ketone, pyridyl.

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Oxidative addition capability of triphosphine iron and ruthenium complexes with methyl iodide

Journal of Organometallic Chemistry ◽

10.1016/j.jorganchem.2003.11.013 ◽

2004 ◽

Vol 689 (4) ◽

pp. 801-810 ◽

Cited By ~ 10

Author(s):

Piotr Jaunky ◽

Helmut W. Schmalle ◽

Montserrat Alfonso ◽

Thomas Fox ◽

Heinz Berke

Keyword(s):

Methyl Iodide ◽

Ruthenium Complexes ◽

Oxidative Addition

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Hydridoiridium(III) sulfoxide complexes and their reactivity toward dioxygen

Canadian Journal of Chemistry ◽

10.1139/v86-148 ◽

1986 ◽

Vol 64 (5) ◽

pp. 897-903 ◽

Cited By ~ 13

Author(s):

Brian R. James ◽

Robert H. Morris ◽

Pal Kvintovics

Keyword(s):

Hydrogen Peroxide ◽

Oxidative Addition ◽

H Nmr ◽

Rate Determining Step ◽

Free Hydrogen ◽

Synthetic Routes

Synthetic routes to hydridoiridium(III) dimethylsulfoxide complexes via oxidative addition of HCl or H2 to precursor insitu iridium(I) species are described. The complexes, trans, mer-IrHCl2(DMSO)3 (1a) and cis, mer-IrH2Cl(DMSO)3 (2), have been characterized by 1H nmr and ir, and contain only S-bonded sulphoxide, DMSO. Comparison is made with data for other isomers reported in the literature, and some discrepancies are discussed. The decomposition of 1a and 2 in chloroform leads to isomers of IrCl3(DMSO)3, while (2) with HCl generates cis,cis IrHCl2(DMSO)2(DMSO) with the O-bonded sulfoxide trans to hydride. The reaction of 1a in dichloromethane with dioxygen occurs with a 1:1 stoichiometry and generates two complexes tentatively formulated as Ir(OH)Cl2(DMSO)2H2O (3) and IrCl2(O2)(DMSO)2DMSO (4); a hydroperoxide intermediate (Ir—OOH) initially formed from 1a is considered to react with further 1a in the rate-determining step. Oxidation of coordinated DMSO to the sulphone is not observed, implying that such a catalyzed O2-oxidation reported earlier in aqueous 2-propanol proceeds via reaction of IrOOH with free DMSO, or else via free hydrogen peroxide.

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