Abstract
The exchange of two phosphine ligands in the metal dimer [Mo 2Cl4{H2P-(CH2)2-PH 2}2] was studied by means of DFT calculations with the B3LYP functional. A dissociative mechanism was fully characterized (minima, transition states) for the reaction that transforms the α isomer with two chelating diphosphines into the β isomer with two bridging diphosphines. It is essentially a two-step mechanism, each step involving the breaking of a Mo-P bond at a metal centre, followed by the formation of a new Mo-P bond with the other metal centre. This Mo-P bond exchange processes are found to be accompanied by the migration of a chloride ligand in the opposite direction. The activation energy computed at the unrestricted UB3LYP-bs level (24 kcal mol-1) is found to be in the range of experimental values.
Original language | English |
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Pages (from-to) | 1494-1498 |
Journal | New Journal of Chemistry |
Volume | 28 |
Issue number | 12 |
DOIs | |
Publication status | Published - 1 Dec 2004 |