CH302 OCTOBER NOV 2020 asssignments

Ass 1
1. (a) Sketch out the structure of the following transition metal complexes as
accurately as possible and clearly show the electron counting (including
the oxidation state of the metal center and ligand charges if present).
(i) [Co(CH3)3Cl3]3− [3 marks]
(ii) CpW(NO)(CO)(PR3) [3 marks]

(b) Consider the isocyanide (C≡NR, sometimes called isonitrile) and nitrile
(N≡CR) ligands that are isomers of one another.
(i) Sketch a Lewis dot diagram for each showing the location of
the lone pair(s) and any formal charges based on organic valence
conventions. [8 marks]
(ii) Which ligand is the better σ-donor? Why? [3 + 3 marks]

2. (a) For each of the following pairs of metal complexes, indicate the one that
will have the highest CO stretching frequency and briefly discuss your
reasoning in each case
(i) PtCl4(CO)2 -or- [PtBr3(CO)]− [4 marks]
− −
(ii) [Co(CO)4] -or- [V(CO)6] [4 marks]
(b) Sketch the structure of Cp2Ta(CCH3) as accurately as possible and
clearly show the electron counting (including the oxidation state of the
metal center and ligand charges if present) [6 marks]

(c) Describe the bonding of alkenes ligands in organometallic complexes

[6 marks]

3. (a) Consider the following reactions. Sketch the final product clearly
showing the structure and geometry. The reaction steps listed may not be
in the correct order. If they are NOT in the correct order please include a
brief and clear explanation of the correct order of steps and why they go in
that order.
(i) [Fe(CO)4]2− + CH3Br → (oxidative addition). [6 marks]

(ii) [Ru(PMe3)(CO)4(acyl)]+ → (elimination, ligand dissociation).

[6 marks]
(b) Distinguish between alkyl phosphines and phosphites in terms of donor
abilities and physical properties. [8 marks]
4. (a) How are IR stretching frequencies used to distinguish bonding modes of
carbonyl ligands [10 marks]
(b) For the following pair of complexes, which will have the highest
average CO infrared stretching frequency? Briefly explain your reasoning.
Cr(CO)3(PMe3)3 - or - MnCl(CO)5 [1+3 marks]
(c) Sketch out the structure of Cp2Co as accurately as possible and clearly show
the electron counting (including the oxidation state of the metal center and
ligand charges if present). [3+3 marks]
5. (a) Consider the isocyanide (C≡NR, sometimes called isonitrile) and nitrile
(NCR) ligands that are isomers of one another. Which ligand is the better
σ-donor? Why? [1+ 3 marks]
(b) Explain why square-planar d8 complexes of Rh(+1), Ir(+1), Ni(+2), Pd(+2),
Pt(+2), and Au(+3) are stable with 16e- configurations and why they only bind
a fifth ligand weakly (to moderately). [10 marks]

(c) Briefly and clearly explain the nature of the metal-ligand bonding for NCH3
in Re(NCH3)(CH3)(CO)2(PPh3) by indicationg σ-bonding strength, π
donor ability, and π-acceptor ability. [6 marks]

6. (a) Predict and sketch the structure for the transition-metal containing
product for the following substitution reactions using one equivalent of
each of the reactants. State the mechanism and reason(s) for your choice.
(i) CpFe(CH3)(CO)(H2C=CHCH3) + PPh3
[3 + 3 +1 marks]
(ii) ReCl(CO)3(PMe3)2 + CH3− [3 + 3 + 1 marks]

(b) Show the Beta Hydride elimination mechanism. [6 marks]

Ass 2

1. (a) (i) Calculate the ground state term symbol for d4 confuguration.
[4 marks]
(ii) Name and differentiate electronic states M and N

[6 marks]
2
(b) The following are the term symbols for a nd
1
G, 1S, 1D, 3F, and 3P
Given that a d2 has 45 microstates, use all relevant formula to assign J
values and show that all microstates have been accounted for.
[10 marks]

2. (a) Explain why [FeF6]3– is colourless whereas [CoF6]3– is coloured, but

exhibits only a single band in the visible region of the electronic spectrum.
[8 marks]
(b) Write the d orbital configurations and then use the Tanabe-Sugano
diagrams to identify the ground electronic term of
(i) low-spin [Rh(NH3)6]3+,
 (ii) [Ti(OH2)6]3+,

(iii) high-spin [Fe(OH2)6]3+. [3 × 4 marks]

3. For a [Mn(OH2)6]2+ given below use Tanabe Sugano diagrams to

(a) Assign the spectra of the aqua ion. [12 marks]

(b) Estimate the value of B. [4 marks]
(c) Use your results to calculate ΔO . [4 marks]

4. (a) [Cr(OH2)6]3+ ions are pale blue-green but the chromate ion [CrO4]2– is an
intense yellow. Characterize the origins of the transitions and explain the
relative intensities. [8 marks]

(b) Below is a table that summarizes the ML and MS values for all np2
microstate. Resolve the microstate and derive all term symbols for the
configuration.

[12 marks]
5. (a) The Racah parameter B is 460 cm in [Co(CN)6] and 615 cm–1 in
–1 3–

[Co(NH3)6]3+. Consider the nature of the bonding with the two ligands and
explain the difference in nephelauxetic effect.. [8 marks]
(b) [Cr(OH2)6]3+ ions are pale blue-green but chromate ion [CrO4]2– is an
intense yellow. Characterize the origins of the transitions and explain the
relative intensities. [8 marks]
(c) Describe the selection rules used in electronic spectra determinations.
[4 marks]
6. (a) Explain how selection rules are often relaxed in real complexes.
[6 marks]
(b) Some complexes, usually very intensely coloured, owe their colour to
charge-transfer. Use an example to explain how ligand to metal charge
transfer occurs. [6 marks]

(c) Illustrate the microstates for two electrons in an n-d level with L= 0 and S
= 0. [4 marks]

(d) Describe the use of Racah parameters in electronic spectra interpretation.

[4 marks]