期刊
ORGANOMETALLICS
卷 30, 期 19, 页码 5088-5094出版社
AMER CHEMICAL SOC
DOI: 10.1021/om1010512
关键词
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资金
- National Science Foundation [CHE-0328121]
- Chevron Energy Technology Co.
- Center for Catalytic Hydrocarbon Functionalization
- Energy Frontier Research Center [DOE DE-SC000-1298]
We have synthesized and fully characterized the air-stable complex (kappa(2)-acac-O,O)(2)Os-IV(Ph)Cl (Cl-1-Ph; acac-O,O = acetylacetonate), which reacts with C6D6 to generate Cl-1-Ph-d(5) in high yield and catalyzes the H/D exchange reaction between benzene and toluene-d(8) upon heating to 140 degrees C. To our knowledge, this is the first example of stoichiometric and catalytic, homogeneous, intermolecular CH activation of arenes by a discrete Os complex. The reactions show extended induction periods. DFT studies of Cl-1-Ph and cis-(kappa(2)-acac-O, O)(2)Os-III(C6H5)(C6D6) (cis-(C6D6)-2-Ph) found a mechanism involving CH activation by traces of Os(III) and Cl atom transfer between Cl-1-Ph and cis-(C6D6)-2-Ph. Experimental data showing that addition of reductants eliminates the induction periods suggest that CH activation occurs from an oxidation state lower than Os-IV, consistent with the DFT predictions. Consistent with a Cl atom transfer mechanism, the triflate analogue of Cl-1-Ph, OTf-1-Ph, does not undergo a stoichiometric or catalytic reaction with C6D6.
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