title: Computational study of gold-catalyzed homo- and cross-coupling reactions.
abstract: The role of gold as the organizing metal in homo- and cross-coupling reactions is explored in this paper combining DFT calculations with QTAIM, NBO, and the energetic span model analysis. For the gold(III) complex 7, a key intermediate in the experimental oxidative coupling scheme by Zhang et al., we describe the mechanisms corresponding to a cross-coupling after transmetalation with boron compounds and to a homocoupling after transmetalation with the original gold(I) complex 6, a new example of dual role of this metal in homogeneous catalysis. We predict for the first path a two-step transmetalation with a low energy rate-limiting step characterized by a four-center transition structure, where fluorine plays an essential role, followed by a reductive elimination where the C-C bond formation is coupled to the departure of fluorine from the gold center. The homocoupling path follows a similar mechanism, with a two-step transmetalation with interesting changes in bonding around the Au(I) center and a rate-limiting reductive elimination. Our findings on the competition between mechanisms, and the effect of ligands and solvent, agree with the experimental results and provide new insights into the mechanism of gold-catalyzed cross-coupling reactions.
authors.affiliation: Departamento de Química Orgánica, Universidade de Vigo, Campus As Lagoas, 32004 Ourense, Spain. faza@uvigo.es
authors.forename: Olalla
authors.initials: O
authors.lastname: Nieto Faza
authors.forename: Carlos
authors.initials: C
authors.lastname: Silva López
mesh_terms: D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007659:Ketones; D050607:Organogold Compounds