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• W2079288760 abstract "Detailed mechanistic studies are reported on the oxidation of alkanes by aqueous [PtCl6]2−/[PtCl4]2− to alcohols plus alkyl chlorides, via proposed (alkyl)PtII and (alkyl)PtIV intermediates. Reactions of [PtCl4]2− with RI (R = CH3, CH2CH2OH) in water yield [PtCl5R]2−, which were isolated as their NMe4 salts. Kinetic rate laws of their decomposition in aqueous chloride solution to ROH and RCl support SN2 displacement by Cl− or H2O as the mechanism of the last step. erythro- and threo-[PtCl5(CHDCHDOH)]2− are obtained by oxidation of [PtCl3 (trans- and cis-CHDCHD)]− respectively, and react with Cl− with inversion of stereochemistry at carbon, consistent with the SN2 mechanism. [PtCl5(CH2CH2OH)]2− is also obtained by oxidation of Zeise's salt with [PtCl6]2−. Kinetics indicate that attack of water on coordinated ethylene to give a β-hydroxyethyl group precedes oxidation of PtII to PtIV, rather than the reverse order, and that this reaction is a model for the oxidation of (alkyl)PtII to (alkyl)PtIV during alkane functionalization. 195Pt isotopic labeling demonstrates that the oxidation is not accompanied by transfer of the β-hydroxyethyl group from one Pt center to another." @default.
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• W2079288760 date "1995-11-01" @default.
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• W2079288760 title "CH activation by aqueous platinum complexes: A mechanistic study" @default.
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• W2079288760 doi "https://doi.org/10.1016/0022-328x(95)05567-9" @default.
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