Abstract
Detailed mechanistic studies are reported on the oxidation of alkanes by aqueous [PtCl 6] 2−/[PtCl 4] 2− to alcohols plus alkyl chlorides, via proposed (alkyl)Pt II and (alkyl)Pt IV intermediates. Reactions of [PtCl 4] 2− with RI (R = CH 3, CH 2CH 2OH) in water yield [PtCl 5R] 2−, which were isolated as their NMe 4 salts. Kinetic rate laws of their decomposition in aqueous chloride solution to ROH and RCl support S N2 displacement by Cl − or H 2O as the mechanism of the last step. erythro- and threo-[PtCl 5(CHDCHDOH)] 2− are obtained by oxidation of [PtCl 3 ( trans- and cis-CHDCHD)] − respectively, and react with Cl − with inversion of stereochemistry at carbon, consistent with the S N2 mechanism. [PtCl 5(CH 2CH 2OH)] 2− is also obtained by oxidation of Zeise's salt with [PtCl 6] 2−. Kinetics indicate that attack of water on coordinated ethylene to give a β-hydroxyethyl group precedes oxidation of Pt II to Pt IV, rather than the reverse order, and that this reaction is a model for the oxidation of (alkyl)Pt II to (alkyl)Pt IV 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.
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