title: 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.
authors.affiliation: Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, United States.
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Robilotto
authors.forename: Nihal
authors.initials: N
authors.lastname: Deligonul
authors.forename: James B
authors.initials: JB
authors.lastname: Updegraff
authors.forename: Thomas G
authors.initials: TG
authors.lastname: Gray
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D050607:Organogold Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000480:Alkynes; D001386:Azides; D008024:Ligands; D050607:Organogold Compounds; D006046:Gold