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Ring expansion versus exo−endo isomerization in (2-pyridyl)methylenecyclobutane coordinated to hydrido(trispyrazolyl)borate- and cyclopentadienyl-osmium complexes

AuthorsCastro-Rodrigo, Ruth ; Esteruelas, Miguel A. ; López, Ana M. ; López, Fernando; Mascareñas, José L. ; Mozo, Silvia; Oñate, Enrique ; Saya, Lucía
Issue Date2010
PublisherAmerican Chemical Society
CitationOrganometallics 29(10): 2372-2376 (2010)
AbstractThe reactions of (2-pyridyl)methylenecyclobutane with the metal fragments [OsTp(PiPr3)]þ and [OsCp(PiPr3)]þ (Tp = hydridotris(pyrazolyl)borate, Cp = cyclopentadienyl) are shown. Complex [OsTp(κ1-OCMe2)2(PiPr3)]BF4 (1) reacts with the organic substrate to give [OsTp{η2-C(CH2CH2CH2)dCH-C5H4N}(PiPr3)]BF4 (2), which evolves into the cyclopentylidene derivative [OsTp(dCCH2CH2CH2CH-C5H4N)(PiPr3)]BF4 (3) as a result of the ring expansion of the methylenecyclobutane unit of the coordinated substrate. The reaction of (2-pyridyl)methylenecyclobutane with [OsCp(NCCH3)2(PiPr3)]PF6 (4) leads to [OsCp{η2-C(CH2CH2CH2)dCH-C5H4N}-(PiPr3)]PF6 (5). In contrast to 2, complex 5 evolves by means of exo-endo isomerization of the C-C doublebondof the coordinated substrate toafford [OsCp{η2-C(dCHCH2CH2)-CH2-C5H4N}(PiPr3)]PF6 (6).
Description5 páginas, 1 figura, 1 esquema, 1 tabla.
Publisher version (URL)http://dx.doi.org/10.1021/om100243w
Appears in Collections:(IQOG) Artículos
(ICMA) Artículos
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