Zinc complexes of chelating monoanionic N-donors and neutral diphosphine ligands were synthesized by reaction of diethylzinc with 1,3-diketimine, diazabutadiene, and diphosphine ligand precursors. These complexes were reacted with primary phosphines in an attempt to solicit phosphine dehydrocoupling reactivity. In most cases, insoluble zinc-containing precipitates were formed and ligands were liberated. For the most sterically encumbered complex, ( Dipp L)ZnEt (3, Dipp L = [(2,6- i PrC 6 H 3 )NC(CH 3 )] 2 CH − ), a product assigned as the zinc-phosphide ( Dipp L)ZnPHPh (6) was observed but could not be isolated as a pure compound. A new, less bulky β-diketiminate complex ( Tol L)ZnEt (2, Tol L = [(p-CH 3 C 6 H 4 )NC(CH 3 )] 2 CH − ) was reacted with primary phosphines to give a precipitate and the bis(β-diketiminate)zinc complex ( Tol L) 2 Zn (5), an apparent product of comproportionation. ( Mes AI)ZnEt (1, Mes AI = MesNC(Me)(Et)C(Me) = NMes) and 2 were structurally characterized.