Sterically crowded triazenides as novel ancillary ligands in copper chemistry

We have synthesized copper salts MN3RR′ derived from the biphenyl- or m-terphenyl-substituted triazenes Tph2N3H (1a) and Dmp(Tph)N3H (1b) (Dmp = 2,6-Mes2C6H3 with Mes = 2,4,6-Me3C6H2; Tph = 2-TripC6H4 with Trip = 2,4,6-i-Pr3C6H2). The homoleptic copper triazenide [CuN3Tph2] (2a) was obtained in high yield from the metallation of 1a with mesityl copper in n-heptane, while the complex [CuN3(Dmp)Tph] (2b) was generated by the same method in situ only. Reaction of 2a with triphenylphosphane gave the 2:1 adduct [CuN3Tph2(PPh3)2] (3a), regardless of the used complex/donor ratio, while reaction of 2a or 2b with a stochiometric amount of t-butylisonitrile afforded the 1:1 adducts [Tph2N3CuCNtBu] (4a) and [Dmp(Tph)N3CuCNtBu] (4b). All new compounds (except 2b) have been characterized by 1H NMR, 13C NMR and IR spectroscopy, elemental analysis, melting point (not 2a), and X-ray crystallography. The IR spectroscopic examination of the ν(CN) stretch in the isonitrile adducts 4a and 4b revealed the weaker donor character of the supporting triazenido ligands compared to related β-diketiminato ligands.