Gold(iii)–arene complexes by insertion of olefins into gold–aryl bonds

Abstract

The synthesis and characterization of the first gold(iii)–arene complexes are described.

(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

“…In addition, complexes A were shown to possess rich reactivity –. The stability imparted by the (P,C) chelate was also leveraged to prepare and characterize new types of gold(III) species –. A goal is now to apply complexes A in catalysis, taking advantage of their rich and unique behavior.…”

“…The other involves π‐activation of the alkyne at the electrophilic gold(III) center, followed by nucleophilic addition of the electron‐rich arene and protodeauration (mechanism II). All the elementary steps and key intermediates of these two catalytic cycles are precedented in gold(III) chemistry, including C ‐H activation, migratory insertion,, and π‐activation of alkynes . No intermediate could be detected upon NMR monitoring, but based on the stereoselectivity of the reaction in favor of trans addition of the aryl group and H atom across the alkyne, we assume that the transformation proceeds via the outer‐sphere mechanism II.…”

Transmetallation of Bis(6‐diphenylphosphinoacenaphth‐5‐yl)‐Mercury and ‐Tributyltin with Precious Metal Chlorides

“…At present, there is great interest in peri-substituted 8-diorganophosphinonaphth-1-yl and 6-diorganophosphinoacenaphth-5-yl precious metal compounds of Re, [1] Ru, [2,3] Ir, [4] Rh, [5] and particularly, Au, [6][7][8][9][10][11][12][13][14][15][16] which involves the synthesis, bonding analysis and applications in bond activation and catalysis. Often, the synthesis of these compounds entails the oxidative addition of the metal to a C-H [1][2][3][4][5] or C-X (X = halide) bond in peri-position to a structurally directing P atom that takes part in coordination to the precious metal.…”

“…Often, the synthesis of these compounds entails the oxidative addition of the metal to a C-H [1][2][3][4][5] or C-X (X = halide) bond in peri-position to a structurally directing P atom that takes part in coordination to the precious metal. [6][7][8][9][10][11][12][13][14] Recently, we have used the well-defined 5-diorganophosphinoacenaphth-6-yllithium, RLi (1, R = 5-Ph 2 P-Ace-6-), [17] as starting material for the synthesis of two related transmetallation reagents R 2 Hg (2, R = 6-Ph 2 P-Ace-5-) [15] and RSnBu 3 (3, R = 6-Ph 2 P-Ace-5-), [18] which offer the advantage to be nonreductive and bench stable (Scheme 1). [19] The reaction of mercury reagent 2 with (tht)AuCl gave rise to the formation of the complex R 2 Hg•AuCl (4), in which the two transition ARTICLE metals are in close proximity and engage in Au•••Hg metallophilic interaction (Scheme 1).…”

Synthesis, Structure, and Reactivity of an NHC Silyl Gold(I) Complex

“…10 Migratory insertion of alkenes into Au(III)-C bonds were then authenticated. [13][14][15][16][17] Scheme 1. Reaction of methyl propiolate with phosphine versus NHC silyl gold(I) complexes.…”