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Reaction Rate Inside the Cavity of [Ga 4 L 6 ] 12− Supramolecular Metallocage is Regulated by the Encapsulated Solvent
Author(s) -
Norjmaa Gantulga,
Maréchal JeanDidier,
Ujaque Gregori
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905608
Subject(s) - solvent , phosphine , chemistry , supramolecular chemistry , ligand (biochemistry) , molecule , methanol , molecular dynamics , reaction rate , crystallography , computational chemistry , organic chemistry , catalysis , biochemistry , receptor
In the present study the dependence of the reaction rate of carbon‐carbon reductive elimination from R 3 PAu(MeOH)(CH 3 ) 2 (R=Me, Et) complexes inside [Ga 4 L 6 ] 12− metallocage on the nature of the phosphine ligand is investigated by computational means. The reductive elimination mechanism is analyzed in methanol solution and inside the metallocage. Classical molecular dynamics simulations reveal that the smaller the gold complex (which depends on the phosphine ligand size) the larger the number of solvent molecules encapsulated. The size of the phosphine ligands defines the space that is left available inside the cavity that can be occupied by solvent molecules. The Gibbs energy barriers calculated at DFT level, in excellent agreement with experiment both in solution and in the metallocage, show that the presence/absence of explicit solvent molecules inside the cavity significantly modifies the reaction rate.