Chem 400 [PDF]

[Co(NH3)6]2+ has absorption bands at 9,000 and 21,100 cm-1. Calculate ∆0 and B for this ion, using the attached Tanabe

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Chem 400 Inorganic Chemistry Practice Final 1____of 10 2____of 10 3____of 20 4____of 10 5____of 10 6____of 10 7____of 10 8____of 10 9____of 10

Σ_______of 100

Name _________________________________________________________ (please print)

1. Show all the steps (i.e., draw the catalytic cycle) for the Monsanto acetic acid synthesis. Include a detailed description of the processes taking place and point out the rate determining step. (10 points)

1

2. [Co(NH3)6]2+ has absorption bands at 9,000 and 21,100 cm-1. Calculate ∆0 and B for this ion, using the attached Tanabe-Sugano Diagram. Hint: The 4T1g → 4A2g transition in this complex is too weak to be observed. (10 points)

2

3. State the types of isomerism that may be exhibited by the following complexes, and draw structures of the isomers. (4 points each) a.

[Co(en)2(ox)]+

b.

[Cr(ox)2(H2O)2]-

c.

[Co(en)(NH3)2Cl2]2+

d.

[PtCl2(PPh3)2]

e.

[Co(en)3]3+

3

4. Describe the bonding in (η4-C4H4)Fe(CO)3 (i.e., develop MO diagrams for both the C4H4 fragment and the Fe(CO)3 fragment). Explain why the complex is diamagnetic. (10 points)

4

5. Give likely products for the following reactions. Do not forget to assign stereochemistry where appropriate. (2 points each) a.

Fe(H2O)63+ + SCN- →

b.

[(C2H4)PtCl3]- + NH3 →

c.

cis-[RhCl4(H2O)2]- + H2O →

d.

NiCl2 + 2C3H5MgBr →

e.

(η5-Cp)2(CH3)Ta=CH2 + Al(CH3)3 →

6. Give chemical names for the following compounds or ions: (2 points each) a.

[ReH9]2-

b.

Rb[AgF4]

b.

Na[AlCl4]

d.

[Ag(NH3)2][BF4]

e.

[Mn(CN)6]4-

5

7. Carbonic anhydrase II is present in red blood cells and catalyzes the reversible hydration of CO2: H2O + CO2 ↔ [HCO3]- + H+ Based on the schematic representation of the active site in human carbonic anhydrase II (CAII) given below, develop a detailed catalytic cycle for the hydration of CO2 catalyzed by CAII. (10 points): H O Zn2+ N N H

N NH

6

N

NH

8. At low temperature and pressure a gas-phase reaction can occur between iron atoms and toluene. The product A, a rather unstable sandwich compound, reacts with ethylene to give compound B. Compound B decomposes at room temperature to liberate ethylene; at –20 ºC it reacts with P(OCH3)3 to give Fe(toluene)[P(OCH3)3]2, C. Suggest structures for compounds A, B, and C. (10 points)

9. Determine the number of valence electrons in each of the following compounds. Hint: Not all of the compounds obey the 18-electron rule! (2 points each) a. Fe(CO)5

b. [Rh(bipy)2Cl]+

c. [HFe(CO)4]-

d. RhCl(H)2(η2-C2H4)(PPh3)2

e. Fe2(CO)9

7

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