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Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/19520
Title: Preparation of half-sandwich osmium-allyl complexes by consecutive c-c bond formation and c-h bond activation reactions
Authors: Esteruelas, Miguel A.; González, Ana I.; López, Ana M.; Oliván, Montserrat ; Oñate, Enrique
Issue Date: 21-Dec-2005
Publisher: American Chemical Society
Citation: Organometallics 25(3): 693–705 (2005)
Abstract: The vinylidene complex Os(η5-C5H5)Cl(CCHPh)(PiPr3) (1) reacts with MeMgCl to give the osmaindene (2), which isomerizes into the exo-allyl compound Os(η5-C5H5)(η3-CH2CHCHPh)(PiPr3) (3) in refluxing toluene. Treatment of 3 with HBF4·OEt2 leads to the endo-d4-allyl derivative [OsH(η5-C5H5){η3-CH2CHCHPh}(PiPr3)]BF4 (4), which can be also obtained by addition of HBF4·OEt2 to 2. Complex 4 contains the terminal CHPh group of the allyl cisoid disposed to the phosphine. In dichloromethane at 40 °C, it isomerizes into an endo-allyl isomer 5 with the terminal CHPh group cisoid disposed to the hydride. Complex 1 also reacts with EtMgCl. The reaction affords (6), which in toluene at 70 °C is converted into the exo-allyl complex Os(η5-C5H5){η3-CH(CH3)CHCHPh}(PiPr3) (7). Treatment of 7 with HBF4·OEt2 leads to an equilibrium mixture of exo-d4-allyl derivatives of formula [OsH(η5-C5H5){η3-CH(CH3)CHCHPh}(PiPr3)]BF4 (8 and 9). The addition of HBF4·OEt2 to 6 gives an endo-d4-allyl isomer, 10, which is transformed into the equilibrium mixture of 8 and 9 after 7 days in dichloromethane at 40 °C. Treatment of 1 with PhMgCl gives rise to (11), which reacts with HBF4·OEt2 in the presence of acetonitrile to afford stilbene and the solvento complex [Os(η5-C5H5)(CH3CN)2(PiPr3)]BF4 (12). The X-ray structures of 3, 5, and 8 are also reported.
Description: 13 pages, 3 figures, 6 tables.
Publisher version (URL): http://dx.doi.org/10.1021/om050907b
URI: http://hdl.handle.net/10261/19520
DOI: 10.1021/om050907b
ISSN: 1520-5126
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