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(10%) Draw the structures of the following compounds: potassium cis-diamminetetrachloroferrate(III) b. mer-triaquatris(thiocyanato-N)cobaltate(II) c....

1.(10%) Draw the structures of the following compounds:
a. potassium cis-diamminetetrachloroferrate(III)

b. mer-triaquatris(thiocyanato-N)cobaltate(II)

c. iodo(thiocarbonato-O,S)(thiocyanato-S)platinate(II)

2.(10%) Determine the point groups of the following:

(a) cis-[Pt Cl2(NH3)2]

(b) trans-[Pt Cl2(NH3)2]

3.(10%) (a) Draw a fully labeled MO diagram for [W(CO)6]. Include the electrons for the metal, ligand and MO orbitals in your diagram. Indicate clearly on the diagram the energy corresponding to .

4.(10%) Draw and name all of the possible isomers for [CoCl2(en)(NH3)2]. Indicate those that are expected to be optically active.

5.(10%) Design a selective two-step synthesis for cis- and trans-[Pt Cl2(NH3)(PMe3)] starting with [PtCl4]2-

6.(10%) Mukherjee, Lloret, and Mukherjee (pages 4471 – 4480) studied a new ligand, [2,4-ditert-butyl-6-{[(2-pyridyl)ethyl](2-hydroxybenzyl)-aminomethyl}-phenol. They synthesized complexes with Co2+, Ni2+, and Cu2+ and found the following data:
Ion λmax (nm) ε (M–1cm–1) μeff (BM)
Co2+ 750 30 4.4
Ni2+ 680 70 2.9
Cu2+ 770 400 1.3
Is the ligand a weak field or strong field ligand? Explain your reasoning. Pages are in volume 47 of Inorganic Chemistry (2008).

7.(15%) The following rate constants (sec-1) have been reported for the aquation at 25oC of the complexes trans-[CoClL(N4)]n+, where N4 is a tetradentate amine ligand. (Note: L is the leaving group.)

L N4 = cyclam N4 = tet-b

Cl- 1.1 x 10-6 9.3 x 10-4

NCS- 1.1 x 10-9 7.0 x 10-7

NO2- 4.3 x 10-5 4.1 x 10-2

N3- 3.6 x 10-6 2.1 x 10-2

CN- 4.8 x 10-7 3.4 x 10-4

NH3 7.3 x 10-8 ----------

a. What is the intimate mechanism of these reactions? Why? Cite two pieces of evidence to support your answer.

b. For each of the above cases, the aquation product is 100% trans. What does this imply about the stoichiometric mechanism of these reactions?

8.(10%) For each pair of reactions below, state

i. a probable mechanism
ii. the faster reaction in the pair
iii. reasons for your choices

a. [CoF(NH3)5]2+ + [Cr(OH2)6]2+ → [Co(OH2)6]2+ + [CrF(OH2)5]2+ + 5NH4+

[CoBr(NH3)5]2+ + [Cr(OH2)6]2+ → [Co(OH2)6]2+ + [CrBr(OH2)5]2+ +

b. [Co(phen)3]3+ + [Co(NH3)6]2+ → [Co(phen)3]2+ + [Co(NH3)6]3+

[Fe(phen)3]3+ + [Fe(NH3)6]2+ → [Fe(phen)3]2+ + [Fe(NH3)6]3+

a. Is the hexanitritovanadate(III) ion expected to exhibit Jahn-Teller distortion? Explain.

b. Rationalize the trend in each of the following sets of IR CO
stretching frequencies (cm-1):

[Ni(CO)4] 2040
[Co(CO)4]- 1890
[Fe(CO)4]2- 1730
[Mn(CO)4]3- 1670

c. Which of the following is expected to be the more thermodynamically stable? Why?

[CrCl2(en)2]+ or [CrCl3(dien)]

d. The hydrolysis of [CoCl2(en)2]+ is dramatically accelerated by the presence of hydroxide ion, while the hydrolysis of [Co(bipy)2Cl2]+ is only slightly affected in basic solution. Account for these facts.

e. Why are complexes of Cr(III) almost always octahedral instead of tetrahedral?

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