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CC12. Solution to Problems, CC5-CC10

CC12. Solutions to Selected Problems

Problem CC5.2.

a)  The resulting anion has aromatic stability.  It is cyclic, fully conjugated, flat and has an odd number of electron pairs.

b)  Cp anion could bind to a metal through just one pair or through two pairs, but in most cases it will bind via three pairs of electrons.

d)  Valence count on metal:  8

     Count on metal, correcting for +2 charge:  6

      Donated from ligands:  2 x 6 = 12

      Total:  18 

Problem CC5.3.

This problem deals with the "bite angle" of the ligand.  Remember, a chain of atoms becomes more flexible the longer it gets, because of the possibility for rotation around each bond along the chain.   As the two double bonds move further apart from each other (one bond apart in (a), two bonds apart in (b) and three bonds apart in (c)), the chain can "open up" and bind with a more optimal overlap with the metal.

Problem CC7.1.
  1. Zn(II), because it is smaller and less polarizable.
  2. K+, because it is less electronegative.
  3. Fe(III), because of the higher charge.
Problem CC7.2.
  1. Me3P, because phosphorus is larger and more polarizable than nitrogen.
  2. Iodide, which is larger and more polarizable than chloride.
  3. Azide, which has a more polarizable, delocalized pi bonding system.
Problem CC7.3.
  1. ZrO2
  2. CdS
  3. WO3
  4. ZnS
  5. Cu2S
Problem CC7.4.
  1. Hg(I) and Hg(II) are both large, polarizable ions.  They are soft cations and should bind well to soft donors. 
  2. The most common soft donor is a sulfur atom or sulfide ion; in amino acids, that suggests cysteine or methionine.
Problem CC7.5.

Fe(III) is a hard cation and should bind well to oxygen donors.  Enterobactin has several oxygen donors it could provide to the iron.  In fact, there is a pair of OH groups on each of the benzene rings in enterobactin.  These benzene rings with two OH groups next to each other are called "catechols."  Because there are three of these groups in enterobactin, and there is enough space in between for the groups to fold around a central atom, enterobactin is a chelating (hexadentate) donor with a high binding constant.

Problem CC8.1.

Problem CC8.2.

The three orbitals shown above interact a little more strongly with the ligands. The three orbitals shown below interact a little more weakly.

The reason for the difference in the interaction has to do with how close the nearest lobe of a d orbital comes to a ligand.  There are really two possible positions:  the face of a cube or the edge of a cube.  If the ligands are at alternating corners of the cube, then the orbitals pointing at the edges are a little closer than those pointing at the faces of the cube.

Problem CC8.3.

The ligands do not overlap with the d orbitals as well in tetrahedral complexes as they do in octahedral complexes.  Thus, there is a weaker bonding interaction in the tetrahedral case.  That means the antibonding orbital involving the d electrons is not raised as high in energy, so the splitting between the two d levels is smaller.

Problem CC8.4.

 

Problem CC8.5.

Because the d orbital splitting is much smaller in the tetrahedral case, it is likely that the energy required to pair two electrons in the same orbital will be grester than the energy requied to promote an electron to the next energy level.  In most cases, the complex will be high spin.

Problem CC8.6.

The orbitals are shown in order of energy.

Problem CC9.1.

The weaker donors include halides and oxygen donors.  Nitrogen atom donors are mostly a little stronger than that.  The strongest donors include carbon donors, especially with pi bonds.

Problem CC9.2.

Problem CC9.3.

Pi donation raises the t2g electrons (the d electrons of proper symmetry for pi overlap with the ligands in an octahedral geometry).

Problem CC9.6.

Because chloride is a weaker ligand than hydroxide, the d orbital splitting gets smaller.  A d-d transition would involve less energy, so it would move to longer wavelength (red shift).  

Problem CC10.1.
  1. The ions in LiF are both smaller than in KBr, so the force of attraction between the ions in LiF  is greater because of the smaller separation between the charges.
  2. Calcium has a 2+ charge in CaCl2, whereas potassium has only a + charge, so the chloride ions are more strongly attracted to the calcium than to the potassium.
Problem CC10.3.
  1. labile (electrons in higher energy d orbital set)
  2. not labile (all electrons in lower energy d orbitals)
  3. not labile (all electrons in lower energy d orbitals)
  4. labile (electrons in higher energy d orbital set)
  5. labile (electrons in higher energy d orbital set)