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Chemistry 432 Advanced Inorganic Chemistry

Homework 8 - 20 Points
Due: Monday, November, 14th Based on the Reading: Meissler and Tarr (M & T), Chapter 10. 1. (3 points) M & T 10.2 and 10.3 Identify the rst-row transition metal M that satises the requirements given (more than one answer may be possible). (a) [M(H2 O)6 ]3+ having one unpaired electron (b) [MBr4 ] having the most unpaired electrons (c) Diamagnetic [M(CN)6 ]3 (d) [M(H2 O)6 ]2+ having LFSE = 3 5 o . Identify the most likely transition metal M that satises the requirements given: (a) K3 [M(CN)6 in which M is a rst-row transition metal and has three unpaired electrons. (b) [M(H2 O)6 ]3+ in which M is a second-row transition metal and LFSE = 2.5o . (c) Tetrahedral [MCl4 ] which has ve unpaired electrons and M is a rst-row transition metal. (d) The third-row d8 transition metal in the square planar complex MCl2 (NH3 )2 which has two M-Cl stretching bands in the IR. 2. (2 points) M & T 10.1 Predict the number of unpaired electrons for each of the following: (a) a tetrahedral d6 ion (b) [Co(H2 O)6 ]2+ (c) [Cr(H2 O)6 ]3+ (d) a square-planar d7 ion (e) a coordination compound with a magnetic moment of 5.1 Bohr magnetons 3. (2 points) What are the possible magnetic moments of Co(II) in tetrahedral, octahedral and squareplanar complexes? 4. (2 points) M & T 10.7 A compound with the empirical formula F e(H2 O)4 (CN )2 has a magnetic moment corresponding to 2.6667 unpaired electrons per ion. How is this possible? (Hint: two dierent octahedral species are involved, each with a single type of ligand) 5. (3 points) Find the number of unpaired electrons, magnetic moment, and ligand eld stabilization energy for: [C o(CO)4 ] , [Cr(CN)6 ]3 , [MnO4 ] . 6. (2 points) M & T 10.22: Solid CrF3 contains a Cr(III) ion surrounded by 6F ions in an octahedral geometry, all at distances of 190 pm. However, MnF3 is in a distorted geometry, with Mn-F distances of 179, 191 and 209 pm (two of each). Suggest an explaination.

OVER = 1

7. (4 points) Consider square planar ML4 , where L is a simple -donor. Assume that the ligands lie in the xy plane. (a) Draw a molecular orbital diagram for this complex. Draw pictures of each of the ve metal-based molecular orbitals. (b) Explain how your diagram would change if L was a -donor like Cl . (c) Explain how your diagram would change for a -acceptor like CN . (d) Assuming that metal d electrons are happy to ll metal orbitals which are near in energy to unperturbed d orbitals, what is the highest dn conguration you imagine would be favorable? What metal ions are likely to be found in this conguration? 8. (2 points) M & T 10.28: Calculations have been reported on the changes tha occur when the following compounds are oxidized by one electron: [Cr(CO)5 PH3 ] and [Cr(CO)5 NH3 ] (see text for pictures/reference). (a) When these compounds are oxidized, what is the eect on the Cr-0 distances? Explain. (b) When these compounds are oxidized, what is the eect on the Cr-P distance? On the Cr-N distance? Explain.