Cleavage of both C(sp3)-C(sp2) bonds of alkylidenecyclopropanes: formation of ethylene-osmium-vinylidene complexes.
The complex [OsTp(kappa(1)-OCMe)(2)(P(i)Pr(3))]BF(4) [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp(3))-C(sp(2)) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(=C=CHR)(eta(2)-CH(2)=CH(2))(P(i)Pr(3))]BF(4) (R = Ph, CH(2)CH(2)Ph). The process is proposed to take place via metallacyclopropene intermediates stabilized by an ethylene chelation assistant. The driving force for the fragmentation is the high stability of the resulting ethylene-Os-vinylidene species.
Castro-Rodrigo
Ruth
R
Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain.
Esteruelas
Miguel A
MA
López
Ana M
AM
López
Fernando
F
Mascareñas
José L
JL
Oliván
Montserrat
M
Oñate
Enrique
E
Saya
Lucía
L
Villarino
Lara
L
D018360:Crystallography, X-Ray; D003521:Cyclopropanes / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D009992:Osmium / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014753:Vinyl Compounds / Q000737:chemistry*
D003521:Cyclopropanes; D005030:Ethylenes; D009942:Organometallic Compounds; D014753:Vinyl Compounds; D009992:Osmium; C036216:ethylene