Organometallic Chemistry: (Ch.

15, pg 623-664, 705-709)

HW: 3,4,5,7,8,38,52

Week 10-1 Generally defined as compounds that possess a metal-carbon bond but there are exceptions to this definition.

Practical level: 25 Billion dollars were made from O-M processes in 1985. Metal-carbonyls are the most typical O-M complexes. Why is CO such a good ligand when it is such a poor lewis base? Backbonding generates a metal-carbon bond. How can we tell if an O-M compound will be reactive? The 18-electron Rule helps us in 90% of the cases. The 18-electron rule is loosely based on the valence shell: 1-s, 3-p, and 5-d-orbitals = 9 orbitals total. How to count the 18 electrons? We will use the neutral atom method to count electrons. 1)The metal has all its electrons and is neutral. 2)The ligands donate a set number of electrons (Table 15.1). 3)The overall charge either adds e- or removes them. The key feature of this counting method is knowing how many electrons a particular ligand donates. Lets start with the simple 2 e- ligands: carbonyl and phosphine. 2e- each = 18 e-s.

Week 10-2

Now the question is, are the COs terminal or bridging? Two ways to see the difference: IR and structure. IR: free CO 2150 cm-1 terminal 2000 cm-1 bridging 1800 cm-1.

How does the CO bridge the metals and still have back-bonding?

In these compounds, the Mn only shows 2000 peaks, while the Co shows 2000 and 1800 peaks. Structures confirm assignment.

Week 10-3

Now lets consider ionic ligands, such as the halides. The neutral atom counting method treats halogens, hydrogen and alkyl ligands as one electron neutral donors. Think of these ligands as stong electrophiles so they only give up one electron to the metal. Note that CO donates both electrons from its lone pair. One can also count electrons with the Ox. State method.

However, note that when halogens bridge metals then they contribute 3 electrons. M-CL: + M = M-Cl-M 2-Rh = 18 4-CO = 8 2-Cl = 6 32 total, 16e-/Rh Exception to the 18 e- rule
Week 10-4

Hydrogen can be broken when reacting with certain complexes. Co2(CO)8 + H2 Co = 9e4CO = 8eCo- = 1e= 2 HCo(CO)4 Co = 9e4CO = 8eH = 1e-

The hydrogen can either be thought of as H* or H-

Unsaturated organic ligands can bind in two manners.

Note that one bonding method contributes 1 electron while the other contributes 3 electrons. Their names reflect this by being 1-allyl and 3-allyl. This can also be seen for cyclopentadienyl (Cp).

The power of the 18 electron rule can be seen in the W(CO)2(C5H5)2 complex.
Week 10-5

If you count the electrons and assume that the Cps are 5 coordinate then the total electrons are 20. W 2-Cp 2-CO = = = 6e10e4e-

The 18 electron rule would suggest that one Cp only contributes 3 electrons and is bent. This is seen in the xtal structure. So, remember that the 18 electron rule is very helpful but it is ONLY a rule. It helps us but does not have a formal explanation, similar to Lewis dot theory. Metal Carbonyl Complexes: Why are they stable? 1) CO is not a strong Lewis base but it forms strong bonds due to back-bonding. 2) Metals have to be in low oxidation state, often zero for this back-bonding. 3) Often obey the 18 electron rule. How do we make these complexes? Ni0 + 4CO (1 atm, 25 C) = Ni(CO)4 + heat = Ni0

However, iron requires more energy to make it react. Fe0 + 5CO (200 atm, 200 C) = Fe(CO)5

Some metals have to be reduced in the presence of CO. CrCl3 + Al + 6CO = AlCl3 + Cr(CO)6

Substitution reactions with carbonyl complexes:

Week 10-6

Ni(CO)4 + PR3

[Ni(CO)3PR3 + CO(g)] bisbenzenechromium(0) + 6 CO(g)

Cr(CO)6 + benzene = Reduction reactions: Mn2(CO)10 + 2Na0 =

2 Na[Mn(CO)5] = 3 Na2[Fe(CO)4}2-

Fe3(CO)12 + 6Na

Note that the 18 electron rule is still obeyed. Hydride Reactions: The lone pair that is created by the above reduction reactions is very basic and is a good nucleophile.

Note that some organometallic lone pairs are so basic they can deprotonate organic solvents

Nitrosyl Chemistry:
Week 10-7

Mixed carbonyl-nitrosyl complexes are known. They form readily by CO replacement.

However, one can avoid the use of NO (toxic gas) by using NOCl.

NO+ is isoelectronic with CO so it is not surprising that they are similar in their chemistry. NO can bind through either the O or the N but it prefers to bind through the N to avoid a formal positive charge on the oxygen. A difference between NO and CO is that NO can bind to the metal bent and linear. When it is bent, the N is in the sp2 configuration. In this form, it is considered a one electron donor. Think of the radical sharing a bond with the metal. The N is sp in the linear form. In this form it is considered a three electron donor. Think of both the lone pair and the radical contributing to the bond.

The first well characterized complex with a bent NO was Vaskas complex.

Week 10-8

So, how do we determine if the NO will be bent or linear?

The key point will be where will the lone pair live on the complex? If the metal is electron poor, then there will be nonbonding orbitals on the metal to accept the lone pair of the N and hence the NO will be linear (i.e. sp). If the metal is electron-rich, then the metal orbitals will be filled and hence the nitrogen must keep the lone pair (i.e. sp2, bent config.).

This can be seen more clearly in the following comparison.

Week 10-9

Dinitrogen Complexes N2 is isoelectronic with CO and NO+ but for years there were no N2 complexes. This was ascribed to the fact that N2 is not polar and thus not a good pi-acceptor. This is not the case for CO because its antibonding orbital is concentrated on the carbon atom which favors overlap with the metal. Some of the first complexes with N2 were with Ru.

Like oxygen, the nitrogen has a number of binding modes.

This is a critical process because it is the key step of nitrogen fixation in nature.

Week 10-10

N2 + 8H + 8e- + 16 MgATP = 2 NH3 + H2 + 16 MgADP + 16 Pi Fertilizers: Natural source was bird guano from the islands off Peru. Then a german, Haber, developed a process to make NH3 and hence the beginning of the green revolution. Haber Process: N2 + H2 = 2 NH3 Simple reaction but requires 1000 atm, 550 and Fe0/Fe2O3 to occur. Metal Alkyls, Carbenes and Carbynes. This means that one can form metal-carbon single, double and triple bonds.

A common reaction that can occur with a sigma-alkyl complex is a beta-elimination.

In this reaction, the metal pulls off a hydride from the bound alkyl, releasing a alkene. Remember this last reaction because we will talk about the reverse soon.

One can also bind an alkene to a metal in a side-on fashion.

Week 10-11

In this complex the pi orbital donates into the sigma bond of the metal and the metal d-orbitals back-bond into the pi* orbital

Now lets use these simple complexes to help us understand an O-M catalytic reaction: Alkene Hydrogenation

The first catalyst for this reaction was the Wilkinsons Catalyst.

The complex is a sq. planar, 16-electron d8 complex.

Week 10-12

The two critical requirements for a good catalyst. 1)It needs to have an open coordination site. 2)It cant be too stable (hence the 16-electrons). As a ligand adds to the complex, the coordination number increases along with the oxidation state. The concept is that as you add a ligand the metal has to contribute electrons to the new bonds being formed and hence is oxidized, oxidative addition. It then follows that when the ligands leave the metal is reduced to its original oxidation state. [Pt(II)Cl4]2- + Cl2 = [Pt(IV)Cl6]2-

How does the Wilkinson catalyst work?

Week 10-13

First, a phosphine dissociates and a solvent molecules takes its place. This is because the phosphine is sterically large.

Then the hydrogen substrate binds, forming a cis-dihydride.

Then the second substrate, alkene, binds.

At this point, one of the hydrides migrates onto the alkene. This is the ratedetermining step and forms a sigma-alkyl.

Solvent then fills the coordination environment (6C).

Finally, the last hydrogen goes on the substrate and you are left with the original catalyst.

This is better shown as a catalytic cycle.

Week 10-14