The dimeric complexes 2-(isopropylamino)troponate zinc methyl and ethyl [(iPrAT)Zn-R]2 (R = Me (2a), Et (2b)) were synthesized by reaction of (iPrAT)H with dimethyl and diethyl zinc, respectively, in toluene at low temperature. Reacting (iPrAT)H with dimethyl zinc at elevated temperature resulted in the double-substituted complex [(iPrAT)2Zn] (3). Compounds 2a,b, which were investigated by single-crystal X-ray diffraction, are dimeric in the solid state. The metal centers are bridged asymmetrically by two (μ)-oxygen atoms; thus a flat Zn-O-Zn'-O' plane is observed. Compounds 2a,b were used as the catalyst in the intramolecular hydroamination reaction of nonactivated terminal aminoolefins and one aminoalkyne. Good catalytic activities at elevated temperature were observed.