Triamidoamine-supported zirconium complexes have proven to be useful catalysts for a range of bond-forming reactions involving arsines. Readily prepared zirconium complexes, (N₃N)ZrX (N₃N = N(CH₂CH₂NSiMe₃)₂^3-; X = monoanionic ligand) facilitate a variety of bond-forming reactions including stoichiometric insertions, catalytic hydroarsination and an efficient synthesis of arsaalkenes. Previous work has shown that (N₃N)Zr-complexes catalyze dehydrocoupling reactions of various arsines. This discovery led to the investigation of stoichiometric insertions into the Zr–As bond using unsaturated polar molecules. It was observed that CS₂, PhCH₂NC, (1-napthyl)NCS, and PhCN engaged in facile 1,1- and 1,2-insertions. The success of these reactions prompted investigation into catalytic hydroarsination of terminal alkynes. In the presence of the Zr-catalyst, it has been observed that hydroarsination of diphenylarsine and a terminal alkyne proceeds with relatively high yields in the dark. The ease with which insertions into the Zr–As bond occurred also spurred investigation of As=C bond formation. It has been demonstrated that isocyanide insertion products thermally rearrange to generate an arsaalkene-containing ligand. Initial results suggest rearrangements that produce a carbon–arsenic double bond are facile, and current efforts are directed at making this process catalytic.