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An Osmium-Carbene complex with fischer−schrock ambivalent behavior

AuthorsEsteruelas, Miguel A. ; González, Ana I.; López, Ana M. ; Oñate, Enrique
Issue Date2003
PublisherAmerican Chemical Society
CitationOrganometallics 22(3): 414-425 (2003)
AbstractComplex Os(η5-C5H5) Cl(PiPr3)2 (1) reacts with N2CHPh to give the carbene derivative Os(η5-C5H5) (=CHPh)Cl(PiPr3) (2). Complex 2 affords the carbene-plus-organic fragment coupling products Os(η5-C5H5)(η3- CHPhC6H5)(PiPr3) (3), OsH(η5-C5H5)(CH2=CHPh) (PiPr3), (4) and OsH(η5-C5H5){η2-(E)-CHPh=CHC H=CH2}(PiPr3) (5) by reaction with PhLi, MeLi, and CH2=CHCH2MgCl, respectively. In solution, the phenyl groups of 3 exchange their positions. The fluxional process takes place via an alkyl intermediate, which can be trapped as Os(η5-C5H5)(CHPh2)(CO) (PiPr3) (6) under CO atmosphere. In toluene at 60°C, complex 5 evolves into its allyl isomer Os(η5-C5H5){η3- CH2CHCH(CH2Ph)} (PiPr3) (7). Complex 2 also reacts with HBF4 and NaOCH3. The reaction with HBF4 leads to [Os(η5-C5H5)(η3- CH2C6H5)Cl(PiPr3)] BF4 (8), which loses HCl to give the hydride-carbyne derivative [OsH(η5-C5H5)(≡CPh)(Pi Pr3)]+ (9), while the reaction with NaOCH3 affords the carbyne compound Os(η5-C5H5)(≡CPh) (PiPr3) (10). In methanol as solvent, complex 10 evolves into the hydride-alkoxycarbene species OsH(η5-C5H5){=C(OMe)Ph}(Pi Pr3) (11). The reaction of 10 with phenol in pentane leads to OsH(η5-C5H5){CH(Ph)OC6 H4}(PiPr3) (12). The X-ray structures of 3, 5, 7, 9, and 12 are also reported.
Identifiersdoi: 10.1021/om0208826
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ICMA) Artículos
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