Silver(i) and copper(i) complexes supported by fully fluorinated 1,3,5-triazapentadienyl ligands

Abstract

Synthesis of the perfluorinated 1,3,5-triazapentadiene [N{(CF₃)C(C₆F₅)N}₂]H and the use of its conjugate base as a supporting ligand for the isolation of silver(I) and copper(I) complexes are reported. Some of the related chemistry involving [N{(C₃F₇)C(C₆F₅)N}₂]⁻ (that has bulkier –C₃F₇groups on the 1,3,5-triazapentadienyl ligand backbone) is also presented. X-ray crystallographic data show a wide variety of structures ranging from intermolecular, hydrogen-bonded chain structure for [N{(CF₃)C(C₆F₅)N}₂]H with a twisted W-shaped N₃C₂ core, monomeric [N{(CF₃)C(C₆F₅)N}₂]Ag(CN^tBu)₂ and [N{(C₃F₇)C(C₆F₅)N}₂]Ag(CN^tBu)₂ where the κ¹-bonded triazapentadienyl ligand bonding to the metal fragment via the central nitrogen atom, monomeric [N{(CF₃)C(C₆F₅)N}₂]Ag(PPh₃)₂ and [N{(C₃F₇)C(C₆F₅)N}₂]Ag(PPh₃)₂ that feature κ¹-bonded triazapentadienyl ligand bonding to the metal fragment via one of the terminal nitrogen atoms, to that of the monomeric [N{(CF₃)C(C₆F₅)N}₂]Cu(CN^tBu)₂ containing a κ²-bonded triazapentadienyl ligand and a U-shaped NCNCN ligand backbone. The isocyanide adducts show relatively high ν_CN values in the IR spectra.