Gold(I) Complexes [N{(C3F7)C(Dipp)N}2]AuL (L = Ethylene, tert‐Butyl Isocyanide, Tetrahydrothiophene, Triphenylphosphine) and Different Triazapentadienyl Ligand Coordination Modes

Fluorinated 1,3,5-triazapentadienyl ligand [N{(C3F7)C(Dipp)N}2] (Dipp = 2,6-iPr2C6H3) has been used in the synthesis of monomeric gold(I)-ethylene, tBuNC, tetrahydrothiophene (THT), and PPh3 complexes. X-ray crystal structures show a rich diversity of coordination modes in which gold coordinates to the central nitrogen atom of 1,3,5-triazapentadienyl ligand in tBuNCAu[N{(C3F7)C(Dipp)N}2] and (THT)Au[N{(C3F7)C(Dipp)N}2] or one of the two terminal nitrogen atoms in [N{(C3F7)C(Dipp)N}2]Au(THT) and [N{(C3F7)C(Dipp)N}2]Au(PPh3), or to both terminal nitrogen atoms in the chelated [N{(C3F7)C(Dipp)N}2]Au(C2H4). The triazapentadienyl ligand therefore serves as either κ1-N or κ2-NN donor, and the N3C3 backbone adopts either a distorted W- or U-shaped conformation. The gold(I) THT adduct exists as a mixture of two isomers in the solid state, as evident from structural data. The gold(I) atom in tBuNCAu[N{(C3F7)C(Dipp)N}2], (THT)Au[N{(C3F7)C(Dipp)N}2], [N{(C3F7)C(Dipp)N}2]Au(THT), and [N{(C3F7)C(Dipp)N}2]Au(PPh3) display linear geometry, whereas [N{(C3F7)C(Dipp)N}2]Au(C2H4) has a three-coordinate, trigonal-planar gold site. Energies of each [N{(CF3)C(Dipp)N}2]AuL (L = ethylene, tBuNC, PPh3 and THT) in κ2-NN chelating, κ1-N central, and κ1-N terminal coordination modes of triazapentadienyl ligand have also been investigated by using DFT.