Selective Au–C Cleavage in (C^∧N^∧C)Au(III) Aryl and Alkyl Pincer Complexes

Abstract

Treatment of gold(III) pincer complexes (C∧N∧C)*AuX with trifluoroacetic acid (X = C6F5, thiophenyl, Me, Et) or of (C∧N∧C)*AuOAcF with AgOAcF/arylboronic acids leads to the selective cleavage of a C–Au bond under mild conditions to give the bidentate complexes (HC-C∧N)*Au(X)(OAcF) [(C∧N∧C)* = 2,6-(C6H3But)2pyridine]. Alkylation of (C∧N∧C)*Au(OAcF) with AlR3 (R = Me, Et) proved to be a high-yielding route to gold(III) alkyls. Au–C cleavage significantly influences reactivity, e.g., with boronic acids. The photoemission of the cleavage product (HC-C∧N)*Au(C6H4F)(OAcF) is about an order of magnitude more intense than that of its tridentate parent compound.

Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

“…In 2012, Bochmann and coworkers identified the [(C^N^C)AuOH] complex 15 (C^N^C = 2,6-bis(4-tert-butylphenylpyridine)) as as uitable precursor to activate C(sp 2 ) À H, C(sp) À H, and N À Hb onds under mild reaction conditions (Scheme 3). [44] The reaction of the resulting Au III -OH complex with phenylacetylene in the absence of any additive furnished [(C^N^C)Au(CCÀC 6 H 5 )] (16)inexcellent yield.…”

Reductive Elimination Leading to C−C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study

“…Protodeauration of [(C^N^C)AuMe] [22] (1j)w ith HAB 2 in CD 2 Cl 2 gave [(C^N-CH)Au-Me(OEt 2 )] + ,w hich is stable in solution at room temperature for several days. Protodeauration of [(C^N^C)AuMe] [22] (1j)w ith HAB 2 in CD 2 Cl 2 gave [(C^N-CH)Au-Me(OEt 2 )] + ,w hich is stable in solution at room temperature for several days.…”

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

“…We found recently that C^N^C pincer ligands based on the dianionic 2,6-diphenylpyridine framework are capable of stabilizing a number of novel gold(III) compound types 32,33 , including the first examples of gold(III) hydrides and olefin complexes 34,35 . Given the importance of oxygen ligands in oxidations as well as water cleavage reactions, we decided to explore the reactivity of such gold(III) pincer complexes towards oxygen ligands, including possible Au-O2Au-H interconversions.…”