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Cyclometalated (N,C) Au(III) Complexes: The Impact of Trans Effects on Their Synthesis, Structure, and Reactivity.

Marte Sofie Martinsen HolmsenAinara NovaMats Tilset
Published in: Accounts of chemical research (2023)
ConspectusThe early years of gold catalysis were dominated by Au(I) complexes and inorganic Au(III) salts. Thanks to the development of chelating ligands, more sophisticated Au(III) complexes can now be easily prepared and handled. The choice of the ancillary ligand has great consequences for the synthesis, properties, and reactivity of the Au(III) complex in question. Among the major factors controlling reactivity are the "trans effect" and the "trans influence" that a ligand imparts at the ligand trans to itself. The kinetic trans effect manifests itself with an increased labilization of the ligand trans to a given ligand and arises from an interplay between ground-state and transition-state effects. The term trans influence, on the other hand, is a ground-state effect only, describing the tendency of a given ligand to weaken the metal-ligand bond trans to itself. Herein, we will use the term "trans effect" to describe both the kinetic and the thermodynamic properties, whereas the term "trans influence" will refer only to thermodynamic properties. We will describe how these trans effects strongly impact the chemistry of the commonly encountered cyclometalated (N,C) Au(III) complexes, a class of complexes we have studied for more than a decade. We found that the outcome of reactions like alkylation, arylation, and alkynylation as well as halide metathesis are dictated by the different trans influence of the two termini of the chelating tpy ligand in (tpy)Au(OAc F ) 2 (tpy = 2-( p -tolyl)pyridine, OAc F = OCOCF 3 , tpy- C > tpy- N ). There is a strong preference for high trans influence ligands to end up trans to tpy- N , whereas the lower trans influence ligands end up trans to tpy- C . Taking advantage of these preferences, tailor-made (N,C)Au(III) complexes could be prepared. For the functionalization of alkenes at (tpy)Au(OAc F ) 2 , the higher trans effect of tpy- C would suggest that the coordination site trans to tpy- C would be kinetically more available than the one trans to tpy- N . However, due to the thermodynamic preference of having the σ-bonded ligand, resulting from the nucleophilic addition to alkenes, trans to tpy- N , functionalization of alkenes was only observed trans to tpy- N . However, for a catalytic process, the reaction should happen trans to tpy- C , as was observed for the trifluoroacetoxylation of acetylene. When functionalizing acetylene in the coordination site trans to tpy- N , protolytic cleavage of the Au-C(vinyl) bond to release the product did not occur at all, whereas trans to tpy- C protolytic cleavage of the Au-C(vinyl) bond occurred readily, in agreement with the higher trans influence of tpy- C over tpy- N . The large impact of the trans effects in Au(III) complexes is finally exemplified with the synthesis of [(tpy)Au(π-allyl)] + [NTf 2 ] - , which resulted in a highly asymmetric π + σ bonding of the allyl moiety. Here, the bonding is such that the most thermodynamically favorable situation is achieved, with the carbon trans to tpy- N bonded in a σ-fashion and the π-allyl double bond being coordinated trans to tpy- C .
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