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Title

Regioselective addition of dienes to the Cβ-Cγ, double bond of the allenylidene ligand of [Ru(η5- 5H5)(=C=C=CPh2) (CO) (PiPr3)]BF4

AuthorsBaya, Miguel ; Buil, María L. ; Esteruelas, Miguel A. ; López, Ana M. ; Oñate, Enrique ; Rodríguez, J. Ramón
Issue Date2002
PublisherAmerican Chemical Society
CitationOrganometallics 21(9): 18411848 (2002)
AbstractThe Cβ-Cγ bond of the allenylidene ligand of [Ru(η5-C5H5)(=C=C=CPh2)(CO)(P iPr3)]BF4 (1) adds dienes such as isoprene, cyclopentadiene, and 1,3-cyclohexadiene. The reaction with isoprene selectively affords the disubstituted vinylidene derivative [Ru(η5-C5H5)(=C=CCH2C(CH3 )=CHCH2CPh2)(CO)(PiPr3)]BF 4 (2), whereas in the presence of cyclopentadiene a 1:1 mixture of the diastereomers RuR,C S a ,CR b(RuS,C R a ,CS b)-[Ru(η5-C5H5)(=C =CCPh2CaHCH2Cb-HCH=CH)(CO)(Pi Pr3)]BF4 (3) and RuR,CR a,CS b(RuS ,CS a,CS b)-[Ru(η5 -C5H5)(=C=CCPh2Ca- HCH2CbHCH=CH)(CO)(PiPr3)]BF4 (4) is obtained. In contrast to the addition of cyclopentadiene, the reaction with 1,3-cyclohexadiene is diastereoselective and gives only the racemic mixture of one diastereomer: RuR,CR a,CS b(RuS ,CS a,CR b)-[Ru(η5 -C5H5)(=C=CCPh2CaHCH2 - CH2CbHCH=CH)(CO)(PiPr3)]BF4 (5). The structures of 2, 3, and 5 have been determined by X-ray diffraction analysis. In the three cases, the geometry around the ruthenium center is close to octahedral, with the cyclopentadienyl ligand occupying one face.
URIhttp://hdl.handle.net/10261/64988
DOI10.1021/om0109760
Identifiersdoi: 10.1021/om0109760
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ICMA) Artículos
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