Origin of the Rate Acceleration in the C−C Reductive Elimination from Pt(IV)-complex in a [Ga4L6]12− Supramolecular Metallocage
Norjmaa, Gantulga (Universitat Autònoma de Barcelona. Departament de Química)
Maréchal, Jean-Didier (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2021
Resum:	The reductive elimination on [(MeP)Pt(MeOH)(CH)], 2P, complex performed in MeOH solution and inside a [GaL] metallocage are computationally analysed by mean of QM and MD simulations and compared with the mechanism of gold parent systems previously reported [EtPAu(MeOH)(CH)], 2Au. The comparative analysis between the encapsulated Au(III) and Pt(IV)-counterparts shows that there are no additional solvent MeOH molecules inside the cavity of the metallocage for both systems. The Gibbs energy barriers for the 2P reductive elimination calculated at DFT level are in good agreement with the experimental values for both environments. The effect of microsolvation and encapsulation on the rate acceleration are evaluated and shows that the latter is far more relevant, conversely to 2Au. Energy decomposition analysis indicates that the encapsulation is the main responsible for most of the energy barrier reduction. Microsolvation and encapsulation effects are not equally contributing for both metal systems and consequently, the reasons of the rate acceleration are not the same for both metallic systems despite the similarity between them.
Ajuts:	Agencia Estatal de Investigación PID2020-116861GB-I00 Agencia Estatal de Investigación CTQ2017-87889-P
Nota:	Altres ajuts: acords transformatius de la UAB
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Chemistry (Weinheim), Vol. 27, Issue 64 (November 2021) , p. 15973-15980, ISSN 1521-3765

DOI: 10.1002/chem.202102250
PMID: 34545974

8 p, 1.6 MB

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