Sammendrag
The Au(III) complex Au(OAcF)2(tpy) (1, OAcF = OCOCF3; tpy = 2-p-tolylpyridine) undergoes reversible dissociation of the OAcF ligand trans to C, as seen by 19F NMR. In dichloromethane or trifluoroacetic acid (TFA), the reaction between 1 and ethylene produces Au(OAcF)(CH2CH2OAcF)(tpy) (2). The reaction is a formal insertion of the olefin into the Au–O bond trans to N. In TFA this reaction occurs in less than 5 min at ambient temperature, while 1 day is required in dichloromethane. In trifluoroethanol (TFE), Au(OAcF)(CH2CH2OCH2CF3)(tpy) (3) is formed as the major product. Both 2 and 3 have been characterized by X-ray crystallography. In TFA/TFE mixtures, 2 and 3 are in equilibrium with a slight thermodynamic preference for 2 over 3. Exposure of 2 to ethylene-d4 in TFA caused exchange of ethylene-d4 for ethylene at room temperature. The reaction of 1 with cis-1,2-dideuterioethylene furnished Au(OAcF)(threo-CHDCHDOAcF)(tpy), consistent with an overall anti addition to ethylene. DFT(PBE0-D3) calculations indicate that the first step of the formal insertion is an associative substitution of the OAcF trans to N by ethylene. Addition of free –OAcF to coordinated ethylene furnishes 2. While substitution of OAcF by ethylene trans to C has a lower barrier, the kinetic and thermodynamic preference of 2 over the isomer with CH2CH2OAcF trans to C accounts for the selective formation of 2. The DFT calculations suggest that the higher reaction rates observed in TFA and TFE compared with CH2Cl2 arise from stabilization of the –OAcF anion lost during the first reaction step.
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