Compounds of the new tetrafluorophthalimido anion, [C(6)F(4)(CO)(2)N](-), are readily accessible by treatment of tetrafluorophthalimide with either LiNPr(i)(2) or mixtures of NEt(3) and Me(3)ECl (E = Si or Sn), to give C(6)F(4)(CO)(2)N-X (X = Li 3, SiMe(3)4, and SnMe(3)5). The reaction of the trimethylsilyl derivative 4 with AgF leads cleanly to the ion pair complex [Ag(NCMe)(2)][Ag(N(CO)(2)C(6)F(4))(2)] (6·2MeCN), which contains a linear [Ag{N(CO)(2)C(6)F(4)}(2)](-) anion and a tetracoordinate Ag(+) cation. Compound 6 reacts with iodine to give the N-iodo compound C(6)F(4)(CO)(2)NI 7, which crystallises as an acetonitrile adduct. Treatment of 6 with LAuCl affords LAu{N(CO)(2)C(6)F(4)} (L = Ph(3)P 8a, Cy(3)P 8b, or THT 9), whereas the reaction with AuCl in acetonitrile affords the heterobinuclear compound [Ag(MeCN)(2)][Au{N(CO)(2)C(6)F(4)}(2)]·MeCN (10·3MeCN). The tetrafluorophthalimido ligand is not readily displaced by donor ligands; however, the addition of B(C(6)F(5))(3)(Et(2)O) to a diethyl ether solution of 8a leads to the salt [Au(PPh(3))(2)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 11. The analogous reaction of (THT)Au{N(CO)(2)C(6)F(4)} with B(C(6)F(5))(3) in toluene in the presence of excess norbornene (nb) gives [Au(nb)(3)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 12. Compounds 11 and 12 contain a new non-coordinating phthalimido-bridged diborate anion with O-bonded boron atoms. The crystal structures of compounds 2-11 are reported.