Synthesis and Structural Characterization of Copper Complexes Containing “R-substituted” Bis-7-azaindolyl borate ligands

The coordination chemistry of scorpionate ligands based on borates containing the 7-azaindole heterocycle is relatively unexplored. Thus, there is a requirement to further understand their coordination chemistry. This article outlines the synthesis and characterization of a family of complexes containing anionic flexible scorpionate ligands of the type, [(R)(bis-7-azaindolyl)borohydride]–, [RBai]–, where R = Me, Ph and naphthyl. The three ligands were coordinated to a series of copper(I) complexes containing a phosphine co-ligand to form the complexes, [Cu(MeBai)(PPh3)] (1), [Cu(PhBai)(PPh3)] (2), [Cu(NaphthBai)(PPh3)] (3), [Cu(MeBai)(PCy3)] (4), [Cu(PhBai)(PCy3)] (5), and [Cu(NaphthBai)(PCy3)] (6). Additional copper(II) complexes, [Cu(MeBai)2] (7) and [Cu(PhBai)2] (8), were obtained during attempts to obtain single crystals from complexes 4 and 2, respectively. Complexes 7 and 8 were also prepared independently from CuCl2 and two equivalents of the corresponding Li[RBai] salt alongside additional complex, [Cu(NaphthBai)2] (9). The copper(I) and copper(II) complexes were characterized by spectroscopic and analytical methods. Furthermore, a crystal structure was obtained for eight of the nine complexes. In all cases, the boron based ligand was found to bind to the metal centers via a κ3-N,N,H coordination mode.