Azido, Triazolyl, and Alkynyl Complexes of Gold(I): Syntheses, Structures, and Ligand Effects

Abstract

Gold(I) triazolyl complexes are prepared in [3 + 2] cycloaddition reactions of (tertiary phosphine)gold(I) azides with terminal alkynes. Seven such triazolyl complexes, not previously prepared, are described. Reducible functional groups are accommodated. In addition, two new (N-heterocyclic carbene)gold(I) azides and two new gold(I) alkynyls are described. Eight complexes are crystallographically authenticated; aurophilic interactions appear in one structure only. The packing diagrams of gold(I) triazolyls all show intermolecular hydrogen bonding between N-1 of one molecule and N-3 of a neighbor. This hydrogen bonding permeates the crystal lattice. Density-functional theory calculations of (triphenylphosphine)gold(I) triazolyls and the corresponding alkynyls indicate that the triazolyl is a stronger trans-influencer than is the alkynyl, but the alkynyl is more electron-releasing. These results suggest that trans-influences in two-coordinate gold(I) complexes can be more than a simple matter of ligand donicity.

Recent developments in gold(i) coordination chemistry: luminescence properties and bioimaging opportunities

“…11). 83 Reaction of [Au(N 3 )(PR 3 )] (R = Ph, Cy) with alkynylfunctionalised coumarins yielded triazolyl-coordinated species with a pendant coumarin fluorophore. From a photophysical perspective, the scope of this synthetic approach is vast, since a range of fluorescent alkynyl derivatives can be imagined that address biocompatibility.…”

Chemistry of gold(I, III) complexes with organic ligands as potential MOCVD precursors for fabrication of thin metallic films and nanoparticles

“…The chemistry of alkynyl complexes of gold(I) was described in several publications [57,64,65]. Alkynyl complexes of Au(I) generally possess relatively high thermal stability (decomposition temperatures are more than 100°С) with a tendency to form alkynyl metal polymers.…”

Fluorescence sensing systems for gold and silver species

“…34 To overcome this drawback, at present, the development of Au(I) complexes for bioimaging purpose is pursued by functionalization of Au(I) with fluorescent ligands, typically known organic fluorophores. 35,36 Ott and Pope investigated a series of linear Au(I) complexes incorporated with an ancillary phosphine, alkynyl, thiolated fluorophore, or anthraquinone (Fig. 3).…”