Chapter 12- Coordination Chemistry and Structure

(HW: 1,9,10,12,15,34) Week 8-1

Coordination Number 1: Very few examples. Here is an organometallic example with Cu(I) and Ag(I).

Coordination Number 2: Few examples. Typical metals that have 2: Cu(I), Ag(I), Au(I), Hg(II) But, they can easily go to 4C [Cu(NH3)2]+ = [Cu(NH3)4]+ The metals are all d10, so preference to go Td. Coordination Number 3: 3C is not very common in nature.

Typically, odd symmetry in nature is rare.

Note that this symmetry was found in a protein, MerR, that is involved in mercury detoxification.

Coordination Number 4
Week 8-2

Td will be favored if there are highly charged ligands and if they are large, I- is typical of this. Also, if there is no CFSE, Td is preferred (d10, d5 h.s., d0) Note, the most important aspect of the chapter is the concept of ISOMERS. Td isomers are optically active (chiral), however, very labile and rarely isolated.

Square Planar Complexes: They are less favored sterically than Td and can be eliminated if ligands are too large. Pd2+, Pt2+, and Ni2+ with strong, non-bulky ligands form sq. planar complexes. They are enhanced by pi interactions, which compensate for the loss of the Oh symmetry. cis-(NH3)2M(Cl)2 has a dipole moment even though it is neutral and is more soluble in water than the trans-complex.

These complexes are geometrical isomers.

They are only optical isomers only if they are asymmetrical. How can we determine which of these two structures is correct?
Week 8-3

The data show that the product is optically active Only the sq. planar complex is chiral, the Td is not due to the mirror plane in the plane of the board.

Coordination Number 5 The two common structures of 5C are the following:

(axial versus equatorial ligands)

(apical versus planar ligands)

Note that 5C complexes are inherently unstable complexes. If electrostatic interactions were the only factor then two 5C complexes would disproportionate into one 4C and one 6C. However, covalency comes into play and hence 5C are found. The energy difference between sq. pyramidal and trigonal bipyramidal is very small. The counter anion can be enough to convert the two structures as they crystallize.

Coordination Number 6:

Most common geometry

3 6

Week 8-4

Octahedral- d and d are predominately this geometry. Geometric isomers of 6C.

Optical Isomers of 6C. Think of the fins of a propeller.

The two isomers are either delta ( ) or lambda ( )

Coordination Number 7: These are very uncommon.

Week 8-5

C7 is awkward geometry for first row transition elementstoo much steric bulk, space problem.

The bigger the atom the more likely to have greater then 6C geometry.

Coordination Number 8: This coordination is not seen in first transition series. It is seen in lanthanides and actinides. Coordination Number 9: All lanthanides are nana-aquo, [Ln(H2O)9]3+ Lanthanides are used in MRI imaging agents, with Gadolinium(III) having a large magnetic moment, f7

Linkage Isomerism NO2 can bind to the metal in 2 different ways, thru O or N. This difference can affect their reactivity.
-

Week 8-6

Electronic Effects Depending on the trans ligand, the atom that binds to the metal can change.

If Phosphorous is bound then it pulls on the metal d-orbital making S bonding less likely (S uses d-orbital bonding). If ammonia is bound then d-orbital is available for Sulfur binding. Can also think of this as a push pull of hard-hard(H3N-Pt or Pt-NCS) and soft-soft (Pt-SCN or H3P-Pt)

Chelate effect:
Week 8-7

We have seen many occasions of ligands being chelates. One of the classic examples are the crown ethers. These ligands can selectively bind cations due to size. 15-Crown-5 prefers Li+ 18-Crown-6 prefers Na+ 21-Crown-7 prefers K+

Oxidation States and their Reduction Potentials: (Ch. 10, HW; 7,8 and pgs 378-381 and Ch. 14, HW; 9,29 and pgs 588-599) Does the redox potential of a metal depend on the d-configuration? d2-configuration: Ti2+ is strong reductant V3+ is not as strong a reductant Fe6+ is a very strong oxidant

There is no correlation between d-configuration and redox potential. The redox potential tells us whether metal will be an oxidant or a reductant.
Week 8-8

What are some of the rules that help us understand electrochemistry? 1) The arbitrary standard is that at 1 M H+, and 1 atm of H2 then H+ + 1e- = 1/2H2 E = 0

Therefore, if a metal will reduce protons to hydrogen gas there has to be a thermodynamic driving force. 2) G = -nFE The E must be positive for the reaction to be spontaneous (- G). When comparing two reactions, the difference in E must be positive for the reaction to be spontaneous. For example, will the following reaction proceed? Zn 0 = Zn2+ + 2e2H+ + 2e- = H2 Zn0 + 2H+ = H2 + Zn2+ 3) The Nerst equation: E = E RT/nF(lnQ), Q = Prod/React This equation helps you determine if a change in the reaction conditions will change the direction of an electrical reaction. For example, with the reduction of water to hydrogen, how will the reduction potential change with acid concentration? E = 0.76 E = 0 G = -2F(0.76) G = -2F(0) G = -1.52F

As the [H+] decreases, the Q gets bigger and E goes more negative (or less spontaneous because G becomes more positive. 4) How do we calculate the skip-step potential?
Week 8-9

Remember that we cant add Es but we can add G One can also do this for reactions in an additive manner. MnO4- + 1eMnO42- + 2eMnO4- + 3e= MnO42- E = +0.90 = MnO2 E = +2.09 = MnO2 G = -1F(+0.90) G = -2F(+2.09) G = -5.08F

E = -(-5.08F)/3F = +1.70V This is presented to you as a Latimer diagram. The main purpose of this chapter is to know how to use Latimer diagrams and to know how to construct one.

Now we want to be able to answer two questions: Will the compound oxidize water or reduce protons to H2? HMnO4- + 3H+ +2e- = MnO2 + 2H2O E = +2.09 + H 2O = 1/2O2 + 2H + 2e- E = -1.23 2+ HMnO4 +H = MnO2 +1/2O2 + H2O E = -(-1.72F)/2F = +1.03V G = -2F(+2.09) G = -2F(-1.23) G = F(-1.72)
Week 8-10

The positive E indicates that MnO42- is not stable in acid! Will it be more stable at pH 7? Yes it will, less H+ Note that the E for water oxidation also varies with acid concentration (like water reduction). Another example of proton reduction to hydrogen. Mn(s) 2H+ + 2eMn(s) + 2H+ = Mn(II) + 2e= H2 = Mn(II) + H2 E = +1.18 E = 0.00 G = -2F(+1.18) G = -2F(0.00) G = F(-2.36)

E = -(-2.36F)/2F = +1.18V Finally, if you are given a partial Latimer diagram you will be required to determine the missing connections of redox potential.