The migrative insertion of CO into the Ni-CH=CH2 bond has been investigated by both static and dynamic density functional methods. The stationary points of the potential surface for the migrative insertion of CO into the Ni-CH=CH2 bond have been characterized using Cl(CO)(2)Ni-CH=CH2 as a model compound. Such a reaction has been found exothermic by 16 kJ mol(-1), with an energy barrier of 9 kJ mol(-1). Dynamic simulations have also been performed on Cl(CO)(2)Ni-CH=CH2 and show that the migrative insertion begins from the cis isomer and occurs via a simultaneous detachment of the vinyl group from the metal and formation of the vinyl-carbonyl bond. (C) 1998 Elsevier Science B.V. All rights reserved.
A dynamical density functional study of CO migration in the Reppe carbonylation
De Angelis, F.;Re, N.;Sgamellotti, A.;Selloni, A.;
1998
Abstract
The migrative insertion of CO into the Ni-CH=CH2 bond has been investigated by both static and dynamic density functional methods. The stationary points of the potential surface for the migrative insertion of CO into the Ni-CH=CH2 bond have been characterized using Cl(CO)(2)Ni-CH=CH2 as a model compound. Such a reaction has been found exothermic by 16 kJ mol(-1), with an energy barrier of 9 kJ mol(-1). Dynamic simulations have also been performed on Cl(CO)(2)Ni-CH=CH2 and show that the migrative insertion begins from the cis isomer and occurs via a simultaneous detachment of the vinyl group from the metal and formation of the vinyl-carbonyl bond. (C) 1998 Elsevier Science B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
