Let us examine each complex using Valence Bond Theory:
- [Ni(NH3)6]2+: The central metal ion is Ni2+ with a 3d8 configuration. To form an octahedral complex, the two 4d orbitals are used for hybridization, resulting in sp3d2 (outer orbital complex). It has two unpaired electrons in the 3d level, making it paramagnetic.
- [Zn(NH3)6]2+: The central metal ion is Zn2+ with a 3d10 configuration. It uses outer 4d orbitals for sp3d2 hybridization (outer orbital complex), but all electrons are paired, making it diamagnetic.
- [Cr(NH3)6]3+: The central metal ion is Cr3+ with a 3d3 configuration. The two inner 3d orbitals are available for d2sp3 hybridization (inner orbital complex). It has three unpaired electrons, making it paramagnetic.
- [Co(NH3)6]3+: The central metal ion is Co3+ with a 3d6 configuration. Ammonia (NH3) acts as a strong field ligand, forcing electrons to pair up. This makes two inner 3d orbitals available for d2sp3 hybridization (inner orbital complex) and results in zero unpaired electrons, making it diamagnetic.
Therefore, [Ni(NH3)6]2+ is the only complex that is both an outer orbital complex and paramagnetic.