Formation of an Asymmetric Acyclic Osmium-Dienylcarbene Complex
Autores: Tamara Bolaño, Ricardo Castarlenas, Miguel A. Esteruelas y Enrique Oñate
Ref. revista: Organometallics, 27, 6367-6370, (2008)
The styryl-allenylidene complex [Os{(E)-CHdCHPh}-(dCdCdCPh2)(CH3CN)2(PiPr3)2]BF4 (2) reacts with HBF4 to
giVe the styryl-alkenylcarbyne [Os{(E)-CHdCHPh}(tCCHdCPh2)(CH3CN)2(PiPr3)2](BF4)2 (3), which in acetonitrile eVolVes
into the dienylcarbene deriVatiVe [Os{dC[(E)-CHdCHPh]-CHdCPh2}(CH3CN)3(PiPr3)2](BF4)2 (4) by means of the concerted
migration of the styryl ligand from the metal center to the carbyne CR atom. A kinetic study and DFT calculations on the transformation of 3 into 4 are reported.
The styryl-allenylidene complex [Os{(E)-CHdCHPh}-(dCdCdCPh2)(CH3CN)2(PiPr3)2]BF4 (2) reacts with HBF4 to
giVe the styryl-alkenylcarbyne [Os{(E)-CHdCHPh}(tCCHdCPh2)(CH3CN)2(PiPr3)2](BF4)2 (3), which in acetonitrile eVolVes
into the dienylcarbene deriVatiVe [Os{dC[(E)-CHdCHPh]-CHdCPh2}(CH3CN)3(PiPr3)2](BF4)2 (4) by means of the concerted
migration of the styryl ligand from the metal center to the carbyne CR atom. A kinetic study and DFT calculations on the transformation of 3 into 4 are reported.