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A neutral macrocyclic ligand with four donor atoms produces a violet, paramagnetic, high-spin complex of NiĀ²+with two anionic (SCN-) ligands. When thiocyanate is replaced by two weakly coordinating perchlorate ions, the complex turns red and becomes low-spin. Draw the crystal field splitting pattern of the d-orbitals in each complex: (1) label each orbital and its energy relative to the barycenter, and (2) include the proper number of electrons. Calculate the CFSE of each complex, show the full calculation not just the final value. However, you don't have to calculate the value for pairing energy, just indicate if it needs to be included or not. High-Spin Complex Low-Spin Complex Barycenter CESEUS: CFSELs: a. Please use the diagram above to explain the color change from violet to red for the high-spin vs low-spin complexes. Consider the following in your discussion: a t2g Es transition should be Laporte forbidden because there is no change in the symmetry of the orbitals involved. However, many transition metal complexes have beautiful colors due to the t2g Ee electronic transition. From an ligand field theory standpoint, what phenomenon(a) allows the t2g estransition to be stronger than predicted in colorful transition metal complexes? b. Assume the high-spin macrocyclic Ni2+ complex above was prepared from [Ni(NH3) 672+ via a square pyramidal intermediate. Calculate the OSSE and use this value to discuss if the ligand substitution reaction is likely to proceed at an appreciable rate. What other crucial factor influences the likelihood of this reaction? Hint: why would the reverse reaction be MUCH more difficult to achieve than the forward reaction?

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