Solutions to Problem set # 2 1. For the compound XeF2: a.

Sketch the group orbitals for the fluorine atoms (with the z axes collinear with the molecular axis). Answer:

B3u

B2g

B2u

B3g

Ag

B1u

Ag

B1u

b. For each of the group orbitals, determine which outermost s, p, and d orbitals of xenon are of suitable symmetry for interaction and bonding. Answer: XeF2 belongs to the Dh group but is more conveniently treated as a D2h symmetrical molecule (see lecture notes for CO2). The 5s, 4dz2, and 4dx2-y2 orbitals of Xe have the Ag symmetry; the 5px,y,z orbitals have the B3u, B2u, and B1u symmetries, respectively. Finally, the 4dxy, 4dxz, and 4dyz orbitals of Xe have the B1g, B2g, and B3g symmetries, respectively. For example, the following combinations are possible:
x dz2 z ag b3u b2g y Only one orbital of Xe, dxy does not have a matching symmetry group orbital of the fluorine atoms. px dxz

2. Describe the bonding in SO3 by using group theory to find the molecular orbitals. Include both the and orbitals, and try to put the resulting orbitals in approximate order of energy.

Answer: SO3 is isoelectronic with BF3 (24 valence electrons) and has molecular orbitals similar to those of BF3, described in Lecture 19. 3. Use molecular orbital arguments to explain the structures of the cyanate, [OCN], and isocyanate, [ONC], ions and compare the results with the electron-dot pictures (Lewis structures). Answer: The cyanate and thiocyanate ions have16 valence electrons and their molecular orbitals are similar to those of CO2 (16 v.e.). See Lecture 20 for more details on the molecular orbital diagram for CO2. The Lewis resonance structures for the two ions show two -bonds (e.g. O=C=N -O-CN). This is in agreement with the presence of two -bonding MOs in the MO description. 4. The thiocyanate ion, SCN, can form bonds to metals through either S or N. Give examples of metal ions which should bind to S and also examples of metal ions which should prefer binding to N. Answer: Soft metal Lewis acids (e.g. Ag(I), Pt(II)) should bind through sulfur; hard metal Lewis acids (e.g. Ti(IV) or Fe(III)) should bind through nitrogen. What is the likelihood of cyanide, CN, forming bonds to metals through N as well as C? Answer: The CN- orbitals are similar to those of CO, but with less difference between the C and N atomic orbital energies than between C and O atoms. As a result, the HOMO should be more evenly balanced between the two atoms and bonding at both ends seems possible, although the majority of known structures have M-CN bonding. 5. The ion NO can react with H+ to form a chemical bond. Which structure is more likely, HON or HNO? Explain your reasoning. Answer: The highest occupied orbitals of NO- are anti-bonding (*) and are expected to have a greater contribution from the p orbitals of the less electronegative nitrogen. Therefore the electron density of the HOMOs is more on the nitrogen side, which should make binding of H+ to N more likely to give a bent molecule H-N=O. 6. AlF3 is insoluble in liquid HF, but dissolves if NaF is present. When BF3 is added to the solution, AlF3 precipitates. Explain. Answer: AlF3 + NaF Na[AlF4] (soluble in HF!) Na[AlF4] + BF3 AlF3 (insoluble in HF) + Na[BF4] 7. CsI is much less soluble in water than CsF, and LiF is much less soluble than LiI. Why?

Answer: Li+ is a hard Lewis acid and has a stronger bond to the hard base F- in LiF. The opposite is true for Cs+ which is a relatively soft acid and has a stronger bond with the soft base I-. 8. Choose the stronger acid or base in the following pairs and explain your choice: a. CH3NH2 or NH3 in reaction with H+? Answer: CH3NH2 is a stronger base (for electronic reasons) b. Pyridine or 2-methylpyridine in reaction with trimethylboron Answer: Pyridine is a stringer base (for steric reasons) c. Triphenylboron or trimethylboron in reaction with ammonia. Answer: Trimethylboron is a stronger acid (for steric reasons).