Tutorial 3

Questions & Answers

CHM 102A: General Inorganic Chemistry

Topics covered:

1) Bio-Inorganic Chemistry (Hemo/Myoglobin and Hemocyanin)

2) Electron Count, ligand types and hapticity
3) Elementary reactions and catalysis

1. Binding of O2 at the active site of hemocyanin is given below

a. What is the oxidation of states of metals in structures A and B? justify your

answer.

b. What is the bond order of O-O in structure B? justify your answer.

Answer: (a) Structure A has Cu(I)&Cu(I) and Structure B has Cu(II)&Cu(II). The Cu(I)
centers oxidized to form Cu(II) during the reaction with O2.

(b) The bond order of O-O in structure B is 1 (peroxo species). Dioxygen reduction
results in the formation of peroxide, which binds to two Cu(II) centres.

2. CO is well known to be strong inhibitor of O2 binding by myoglobin and hemoglobin,

yet relative to O2 its binding is much weaker in the protein compared to a simple Fe-
Porphyrin complex. This suppression of CO binding is important as even trace levels
of CO would otherwise have serious consequences for aerobes. Suggest an
explanation.

Answer: The binding of O2 is nonlinear and the distal O atom is well positioned to form
a hydrogen bond to the distal imidazole. By contrast, CO adopts a linear Fe-C-O
bonding arrangement and does not participate in the additional H-bonding. Hence,
reduces its efficiency to myoglobin and hemoglobin compared to a simple synthetic
Fe-Porphyrin complex.
3. Identify the first-row transition metal for the following 18-electron species:

a) [M(CO)3(PPh3)]–, b) HM(CO)5, c) (η4-C8H8)M(CO)3 and (d) [(η5-C5H5)M(CO)3]2

(assume single M-M bond)

Answer:

(a) [M(CO)3(PPh3)]–:

Ligand contribution to electron count: 3*2 e- + 1*2 e- = 8e-

Need 18 – 8 = 10 electrons for M–, So the metal is Co.

(b) HM(CO)5

Ligand contribution to electron count: 5*2 e- + 1*2 e- = 12e-

Need 18 – 12 = 6 electrons for M+, So the metal is Mn.

(c) (η4-C8H8)M(CO)3:

Ligand contribution to electron count: 4 e- + 3*2 e- = 10e-

Need 18 – 10 = 8 electrons for M, So the metal is Fe.

(d) [(η5-C5H5)M(CO)3]2:

Ligand contribution to electron count: 6 e- + 3*2 e- + 1 (M–M) = 13 e-

Need 18 – 13 = 5 electrons for M+, So the metal is Cr.

4. Compounds A and B in the given equation obey the 18-electron rule.

Cp2Zn + Et2Zn → [CpZn]2 + CpZnEt

A B

Draw the structures of compounds A and B clearly indicating hapticity of Cp. Also
indicate oxidation state of Zn in both A and B

Ans:
5. Infra-red spectral analysis of the following three complexes showed a set of two IR
bands for the υCO stretching frequencies. Match the correct set of IR bands to the given
compounds and justify your reason for the assignment.

(a) (η5-C5H5)2Ti(CO)2

(b) (η5-C5Me5)(η5-C5H5)Ti(CO)2

(c) (η5-C5Me5)2Ti(CO)2

[1956 & 1875 cm-1 ; 1930 & 1850 cm-1 ; 1979 & 1897 cm-1]

where (η5-C5H5) = Cp and (η5-C5Me5) = Cp*

Answer: When compared to Cp, Cp* ligand is a better electron donor. As a reflection
of the formal electron density at the titanium centre, the carbonyl IR absorption
frequencies of CpCp*Ti(CO)2 (b) are intermediary (1956, 1875 cm-1, (b)). between
those of Cp2Ti(CO)2 (1979, 1897 cm-1 (a)) and those of Cp*2Ti(CO)2 (1930, 1850
cm-1, (c)).

6. In the given catalytic cycle of hydroformylation, fill in the blanks with the name of the
reactions (boxes adjacent to the arrows) and the structure of the specific intermediate
with the correct geometry at the given step.

7. Calculate TON and TOF of the following reaction.

Ans: TON (turnover number) = (50 mmol/0.001 mmol) x 60/100 = 30000

TOF (turnover frequency) = 30000/25 min = 1200 min-1