CML101: Introduction to Chemistry

Inorganic Chemistry: Tutorial 3

1. Ferrocene itself shows much more chemical stability than cobaltocene and nickelocene. For
example, ferrocene rarely participates in reactions in which other ligands substitute for the
cyclopentadienyl ligand. However, cobaltocene and nickelocene undergo the following
reactions. Explain.

2I
H
("5-C 5H5)2Co + I2 Co Co

("5-C5H5)2Ni + 4 PF3 [Ni(PF3)4] + organic products

2. Four chlorine ligands are missing in each of the given skeletons of dimeric compounds a, b
and c. Given that all of them obey the 18-electron rule and no additional metal-metal bonds are
present, attach the missing Cl ligands on the complexes in the appropriate manner.

3. Draw a stable structure corresponding to the formula [(CO)2Ru(𝜇 -H)(𝜇 -CO)(𝜇 -

Me2PCH2PMe2)2Ru(CO)2]+.
4. Provide plausible reasons for the differences in IR wavenumbers between each of the following
pairs: (a) Mo(CO)3(PF3)3 2040, 1991 cm−1 versus Mo(CO)3(PMe3)3 1945, 1851 cm−1, (b)
Mn(Cp)(CO)3 2023, 1939 cm−1 versus Mn(Cp*)(CO)3 2017, 1928 cm−1.

(a) CO CO
(b)
F3P CO Me3P CO
Mo Mo Mn Mn
F3P CO Me3P CO CO CO
PF3 PMe3 OC CO OC CO
νCO = 2040, 1991 cm−1 νCO = 1945, 1851 cm
−1
νCO = 2023, 1939 cm−1 νCO = 2017, 1928 cm−1

5. Suggest why [V(CO)6] is easily reduced to [V(CO)6]−

 6. Which one of the following complexes is most stable (assuming metal-metal multiple
bonds are absent, W = 5d56s1): W2(CO)10, [W2(CO)10]2−, [W2(CO)10]2+, [W2(CO)10]+, or
[W2(CO)10] −

7. Does CO stretching frequency increase or decrease when (a) L of LnM−CO becomes more
electron withdrawing? (b) CO of LnM−CO becomes coordinated to a Lewis acid, A, to become
LnM−CO−A?
8. Complexes containing Ph2PCH2CH2PPh2, sometimes known as diphos, are abundant.
Using the 18-electron rule as guide, draw the structures of
(a) (OC)5W(PPh2CH2CH2PPh2), (b) (OC)4W(PPh2CH2CH2PPh2),
(c) (OC)4W(PPh2CH2CH2PPh2)2, (d) (OC)10W2(PPh2CH2CH2PPh2),
(e) (OC)8W2(PPh2CH2CH2PPh2)2
9. Infrared spectra of [V(CO)6]− and Cr(CO)6 show absorptions at 1859 and 1981cm−1
respectively, assigned to νCO, and 460 and 441cm−1 assigned to νMC. Give a reason for this.

10. Rationalize the following observations: On forming [IrBr(CO)(𝜂 2−C2(CN)4)(PPh3)2], the

C−C bond in C2(CN)4 lengthens from 135 to 151 pm.
11. The reaction of Mn2(CO)10 with Na/Hg can be monitored by IR spectroscopy in the region
2100–1800cm−1. The starting material and product show absorptions at 2046, 2015 and 1984
cm−1, and at 1896 and 1865 cm−1, respectively. Suggest a likely product of the reaction. Check
that the Mn centre in the product obeys the 18-electron rule. Account for the changes in the IR
spectra.
12. Which of the compounds (I) or (II) will undergo substitution of a CO ligand for a phosphine
more readily?

Re Re
OC CO OC CO
CO CO
(I) (II)
13. The reaction of CoII(TPP) complex with nitric oxide resulted in the formation of Co(TPP)(NO)
adduct, which was characterized by determining the structure of the compound. The N−O bond
length and <Co−N−O bond angle observed in the complex are described below. Draw the structure
of the complex with the oxidation state of the metal ions.
14. The N−O stretching vibration in NO is observed at 1876 cm−1. However, the 𝝂 N−O in
[Ru(NH3)5(NO)]Cl3 complex is observed at 1903 cm−1. In addition, a liner M−N−O bond formation
was noted in the solid-state structure of the complex. Comment on the bonding of NO in the
mentioned complex.
15. In the following complexes, the oxidation state of the metal ions was determined to be +II.
Calculate the number of electrons present at the antibonding orbitals of NO in the complexes.

A B C

{FeNO}8
{FeNO}9 {NiNO}10