Application of Organometallic

Chemistry – Breaking the Inert

C-H Bond

Literature Special Topic

Date

Created by [John Lee, University of Tennessee Chattanooga, John-Lee@utc.edu] and posted on VIPEr
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You want to break which bond!

Example Organic Molecules

-Why do we draw line structures for

Organic molecules?

-High bond energy

methane 100 kcal/mol
benzene 110 kcal/mol

-High pKa
on the order of >40

**,but…Nature uses the C-H bond: See methane monooxygenase and vitamin-b 12
 In organic chemistry….

Generic Substitution Reaction (SN1 shown)

Leaving Groups (LG)

TsO-, NH3 > I-, H2O > Br- > Cl- > HO-, NH2-, RO-

Carey, F. A. Organic Chemistry, 4th ed. 2001, McGraw-Hill,

Chapter 8.
 In organometallic chemistry….

Cross-Coupling Reactions

Heck, R. F.; Negishi, E.; Suzuki, A. palladium catalyzed cross couplings in Organic Synthesis: Great Art in a Test Tube.
http://nobelprize.orglnobeljrizes/chemistry/laureatesl}O10/press.html (March 17, 2011).

but wait I said C-H not C-X activation?

 If it ain’t broke why fix it?

-Nearly everything comes from coal, oil or natural gas

Coal: 1,000 – 2,000 years
Oil: 50 – 150 years
Natural gas: 207 – 590 years

-However this is not sustainable for population growth

Why?

-We are a good 10-20 (optimistic) years from solar

-For the interim time we should use our resources to the

best of our ability
How?

Lewis, N. S.; Nocera, D. G. Proc. Nat. Acad. Sci. 2006, 103,

15729-15735.
 How? Rationale design and synthesis
Metal + Ligands

C-donor,
N-donor,
O-donor,
P-donor,
or S-donor etc…

What it is really all about!

Shriver and Atkins Inorganic Chemistry, 5th ed. 2001, Freeman, Chapter 1.
 Some typical mechanisms

Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507-514.

Example 1: Oxidative addition

Qualitative MO Diagram

-The metal’s oxidation state increases by two units

Must be accessible

-Requires an electron rich metal

Low oxidation state
Electron donating ligands

-The metal’s coordination # increases by two

Must be accessible

-Many d8 metals meet these criteria:

Primarily RhI and IrI
Sometimes PdII and PtII
Example of oxidative addition:
Alkane dehydrogenation
Example 2: -Bond metathesis

Qualitative MO Diagram

-Early transition metals that do not have a n+2

oxidation state available

-Late transition metals that do not have an

accessible n+2 oxidation state

-Many d0 metals meet these criteria:

For example, ScIII, ZrIV, TaV
Example of -bond metathesis:
Hydromethylation of propylene

Sadow, A. D.; Tilley, T. D. J. Am. Chem. Soc. 2003, 125, 7971-7977.

Example #3: Electrophilic substitution

Qualitative MO Diagram

Milstein, D. et al. J. Am. Chem. Soc. 1998, 120, 12539-12544

 Example of electrophilic substitution:
Methane oxidation

Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T; Fuji, H.
Science 1998, 280, 560-564.
C-H Functionalization: A challenge

C-C Bond Formation – Olefin Insertion

Foley, N. A.; Lee, J. P.; Ke, Z.; Gunnoe, T. B.;

Cundari, T.. R. Acc Chem. Res. 2009, 42, 585-597.