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- W2027592759 endingPage "5152" @default.
- W2027592759 startingPage "5140" @default.
- W2027592759 abstract "The hexahydride complex OsH6(PiPr3)2 (1) reacts with 8-methylquinoline and 2-(dimethylamino)pyridine to give (2) and (3), respectively, as a result of the release of two hydrogen molecules of 1 and the C(sp3)−H bond activation of a methyl group of the organic substrates. In solution the hydride ligands and the hydrogen atoms of the methylene group of 2 exchange their positions. The activation parameters for the process are ΔH⧧ = 18.9 ± 0.1 kcal·mol-1 and ΔS⧧ = 3 ± 2 eu. Treatment of 2 with HBF4 affords the hydride-elongated dihydrogen derivative (6), with the methyl group of the quinoline ligand coordinated in a η3-H2C fashion. The X-ray structure of 6 and the DFT optimization of the structure of the model cation [OsH(η2-H2)(CH4)(NH3)(PMe3)2]+ prove that the methyl coordination in the δ agostic complex is similar to the methane coordination in the model compound. The reaction of 3 with HBF4 leads to the cyclic carbene derivative (7), as a result of the release of a hydrogen molecule and a C(sp3)−H bond activation on the methylene group of 3. The formation of 2, 3, 6, and 7 has been analyzed by DFT calculations." @default.
- W2027592759 created "2016-06-24" @default.
- W2027592759 creator A5020144197 @default.
- W2027592759 creator A5067242867 @default.
- W2027592759 creator A5078141702 @default.
- W2027592759 creator A5079497892 @default.
- W2027592759 creator A5090236062 @default.
- W2027592759 creator A5091230523 @default.
- W2027592759 date "2007-09-15" @default.
- W2027592759 modified "2023-10-02" @default.
- W2027592759 title "Coordination and Rupture of Methyl C(sp<sup>3</sup>)−H Bonds in Osmium−Polyhydride Complexes with δ Agostic Interaction" @default.
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