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Formation of cationic half-sandwich osmium-vinylidene complexes from [Os(η5-C5H5)(Pi Pr3)2]+ and terminal alkynes

AuthorsBaya, Miguel ; Esteruelas, Miguel A. ; López, Ana M. ; Modrego, Francisco J. ; Oñate, Enrique
Issue Date2001
PublisherAmerican Chemical Society
CitationOrganometallics 20(20): 4291-4294 (2001)
AbstractAb initio calculations on the model complexes [Os(η5-C5H5)(η2-HC≡CH) (PH3)2]+ (1), [OsH(η5-C5H5)-(C≡CH) (PH3)2]+ (2), and [Os(η5-C5H5)(=C=CH2) (PH3)2]+ (3) indicate that the thermodynamic stability of these compounds decreases according to the sequence 3 > 1 > 2. According to this, the vinylidene complexes [Os(η5-C5H5)(=C=CHR)(Pi Pr3)2] PF6 (R = Cy (8), Ph (9)) are prepared by deprotonation of [OsH(η5-C5H5)(C≡CR)- (PiPr3)2]PF6 (R = Cy (4), Ph (5)) with KOH in methanol and subsequent protonation of the resulting alkynyl derivatives Os(η5-C5H5)(C≡CR)(Pi Pr3)2 (R = Cy (6), Ph (7)). The X-ray structure of [Os(η5-C5H5)(=C=CHPh)-(Pi Pr3)2]PF6 (9) is also reported.
Identifiersdoi: 10.1021/om0104565
issn: 0276-7333
e-issn: 1520-604
Appears in Collections:(ICMA) Artículos
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