The Complex Amide K 2 [Zr(NH 2 ) 6 ]

We present the low‐temperature synthesis of potassium hexaamido zirconate(IV) from the transition metal tetrafluoride and thealkali metal dissolved in liquid ammonia at –40 °C. Potassium hexaamido zirconate(IV) K 2 [Zr(NH 2 ) 6 ] is the first ternary amide reported for elements of group 4 of the periodic table It crystallizes with a novel structure type in the trigonal space group R $\bar{3}$ c with a = 6.5422(2) Å, c = 32.824(2) Å, V = 1216.66(9) Å 3 , Z = 6 and c / a = 5.017. The structure can be derived from the K 2 PtCl 6 type. The compound contains discrete D 3 ‐symmetric [Zr(NH 2 ) 6 ] 2– anions which differ significantly from octahedral shape. Quantum chemical calculations show the distortion to arise from a splitting of degenerate d‐orbitals on the zirconium atom leading to a significant gain in energy.