Formation of an Asymmetric Acyclic Osmium−Dienylcarbene Complex

Formation of an Asymmetric Acyclic Osmium−Dienylcarbene Complex

The styryl-allenylidene complex [Os{(E)-CHCHPh}(CCCPh2)(CH3CN)2(P i Pr3)2]BF4 (2) reacts with HBF4 to give the styryl-alkenylcarbyne [Os{(E)-CHCHPh}(CCHCPh2)(CH3CN)2(P i Pr3)2](BF4)2 (3), which in acetonitrile evolves into the dienylcarbene derivative [Os{C[(E)-CHCHPh]CHCPh2}(CH3CN)3(P i P...

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Veröffentlicht in:Organometallics 2008-12, Vol.27 (23), p.6367-6370
Hauptverfasser: Bolaño, Tamara, Castarlenas, Ricardo, Esteruelas, Miguel A., Oñate, Enrique
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container_issue 23
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container_title Organometallics
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creator Bolaño, Tamara
Castarlenas, Ricardo
Esteruelas, Miguel A.
Oñate, Enrique
description The styryl-allenylidene complex [Os{(E)-CHCHPh}(CCCPh2)(CH3CN)2(P i Pr3)2]BF4 (2) reacts with HBF4 to give the styryl-alkenylcarbyne [Os{(E)-CHCHPh}(CCHCPh2)(CH3CN)2(P i Pr3)2](BF4)2 (3), which in acetonitrile evolves into the dienylcarbene derivative [Os{C[(E)-CHCHPh]CHCPh2}(CH3CN)3(P i Pr3)2](BF4)2 (4) by means of the concerted migration of the styryl ligand from the metal center to the carbyne Cα atom. A kinetic study and DFT calculations on the transformation of 3 into 4 are reported.
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