A Combined Experimental and Density Functional Theory Investigation of Hydrocarbon Activation at a Cationic Platinum(II) Diimine Aqua Complex under Mild Conditions in a Hydroxylic Solvent
| Autor: | Hanne Heiberg, Lars Johansson, Odd Gropen, Olav B. Ryan, Ole Swang, Mats Tilset |
|---|---|
| Rok vydání: | 2000 |
| Předmět: |
chemistry.chemical_classification
Inorganic chemistry Cationic polymerization chemistry.chemical_element General Chemistry Biochemistry Medicinal chemistry Catalysis Methane Solvent chemistry.chemical_compound Colloid and Surface Chemistry Hydrocarbon chemistry Protonolysis Benzene Platinum Dichloromethane |
| Zdroj: | Journal of the American Chemical Society. 122:10831-10845 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja0019171 |
| Popis: | Controlled protonolysis of (Nf-Nf)Pt(CH3)2 (1; Nf-Nf = ArNCMeCMeNAr, Ar = 3,5-(CF3)2C6H3) with HBF4·Et2O in dichloromethane in the presence of small quantities of water gives the BF4- salt of the aqua complex (Nf-Nf)Pt(CH3)(H2O)+ (6). When dissolved in trifluoroethanol (TFE), 6(BF4-) effects the activation of methane and benzene C−H bonds under very mild conditions. Thus, 6 reacted with benzene in TFE-d3 at ambient temperature to quantitatively yield (Nf-Nf)Pt(C6H5)(H2O)+ and methane after 2−3 h. The use of C6D6 led to multiple incorporation of deuterium into the methane produced and suggests the involvement of methane σ-complex and benzene σ- or π-complex intermediates. When the solution of 6(BF4-) was exposed to 13CH4, an exchange reaction produced ca. 50% of (Nf-Nf)Pt(13CH3)(H2O)+ and CH4 after ca. 48 h at 45 °C. The reaction was inhibited by added water, suggesting that water is reversibly lost from 6 before C−H activation takes place. The use of CD4 resulted in multiple deuterium incorporation into t... |
| Databáze: | OpenAIRE |
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