Abstract
To probe the reactivity of gold-nitrogen bonds, we have examined the insertion chemistry with carbon disulfide (CS2) as well as oxidation with cesium tribromide (CsBr3) with Au(I) amidinate complexes. The reaction of Ph3PAuCl with Na[(2,6-Me2C6H3N)2C(H)] yields the mononuclear, two-coordinate gold(I) complex, Ph3PAu[κ1-(2,6-Me2C6H3N)2C(H)], 1. The reactivity of 1 with CS2 produced the mononuclear Au(I) compound, Ph3PAu{κ1-S2C[(2,6-Me2C6H3N)2C(H)]}, 2. In the case of CsBr3 the previously reported dinuclear Au(I) complex, Au[(2,6-Me2C6H3N)2C(H)]2, 3, was isolated with formation of Ph3PBr2. We also compared the reactivity of CS2 and CsBr3 with 3. Carbon disulfide insertion with 3 produces a dimeric product, Aun[CS2(2,6-Me2C6H3NC(H)=NC6H3Me2)]n, 4, featuring a dinuclear core with linking aurophilic interactions, making it appear polymeric in the solid state. When CsBr3 is reacted with 3 the Au(II,II) product is obtained, Au2[(2,6-Me2C6H3N)2C(H)]2(Br)2, 5.
Highlights
The chemistry of gold is dominated by soft donor ligands due to the propensity for gold to form stronger interactions with elements such as phosphorus and sulfur
A rare mononuclear gold(I) amidinate complex has been synthesized from reaction of Ph3PAuCl with Na[(2,6-Me2C6H3N)2C(H)], and its reactivity explored with CS2 and CsBr3
The dinuclear gold amidinate complex was examined with CS2 and CsBr3
Summary
The chemistry of gold is dominated by soft donor ligands due to the propensity for gold to form stronger interactions with elements such as phosphorus and sulfur. Gold-nitrogen bonds are uncommon [1] and the reactivity of these bonds is relatively unexplored [2]. With the recent advances in gold amidinate chemistry [3], we sought to develop this reactivity by examining insertion and oxidative chemistry in Au(I) amidinate complexes. Di- [4,5,6], tri- [4], and tetranuclear [7,8,9,10] gold amidinate complexes have been isolated, but to our knowledge, only one mononuclear gold complex has been reported [11]. The oxidative chemistry of dinuclear Au(I) amidinate complexes is characterized by a two-electron redox process with one-electron being produced from each Au(I)
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have