1. in organometallic chemistry
Hot Topics en Hypes
in organometallic chemistry
5/20/2019
Hot Topics and Hypes

2. Hot Topics Ideal conversions with (nearly) incompatible requirements:
C-H activation
and other "all-in-one" conversions
Selective oxidations
Anti-Markovnikov water addition
(Co)polymerization of functionalized olefins
Chiral conversions
Mechanisms / models of enzymes
5/20/2019
Hot Topics and Hypes

3. Hypes Everything "BIO" and "NANO" Buckyballs, buckytubes
Supramolecular chemistry
Materials
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Hot Topics and Hypes

4. C-H activation Problems: C-H bond is least reactive bond
Product is usually more reactive than starting material
Þ further oxidation
Product is always better donor than starting material
Þ product inhibition
5/20/2019
Hot Topics and Hypes

5. C-H activation
This will not work:
5/20/2019
Hot Topics and Hypes

6. C-H activation This does work: B-B bond weak B-H and B-C strong
product hardly coordinating
5/20/2019
Hot Topics and Hypes

7. C-H activation A real example: Electrophilic attack on C-H bond (?)
5/20/2019
Hot Topics and Hypes

8. CH4 to CH3OH: how does industry do it?
"hot pipes"
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Hot Topics and Hypes

9. CH4 to CH3OH: how does nature do it? (we think)
MMO =
"methane mono-oxygenase"
5/20/2019
Hot Topics and Hypes

10. C-H activation
C-H activation for CH4 ® CH3OH via homogeneous catalysis is "useless"
selective conversion van non-activated C-H bonds in larger molecules is highly desirable
nature does this through "shape selectivity" with e.g. cytochrome P450
zeolites sometimes work quite well
5/20/2019
Hot Topics and Hypes

11. How can you study C-H activation?
"microscopic reversibility"
activation of more reactive C-H bonds
e.g. aromatic Csp2-H bonds
5/20/2019
Hot Topics and Hypes

12. Selective oxidation Epoxidation: does not work for other olefins
(allylic C-H bonds are too reactive)
5/20/2019
Hot Topics and Hypes

13. Selective oxidation Aldehydes / ketones: 5/20/2019
Hot Topics and Hypes

14. Selective oxidation Desired: Current process: hydroformylation
5/20/2019
Hot Topics and Hypes

15. Anti-Markovnikov water addition
Desired:
Current process: via hydroformylation
5/20/2019
Hot Topics and Hypes

16. Anti-Markovnikov water addition
A possible organometallic route:
5/20/2019
Hot Topics and Hypes

17. (Co)polymerization of functionalized olefins
Desired:
Problem:
5/20/2019
Hot Topics and Hypes

18. (Co)polymerisation of functionalized olefins
Possible solutions:
Late transition metal complexes
b.v. Ni/Pd Brookhart
Protection of functional group
Fictionalization after polymerization
5/20/2019
Hot Topics and Hypes

19. Chiral conversions Noyori / Knowles / Sharpless
Precise tuning needed for every new reaction
combinatorial catalysis?
Few general principles
Many "standard" chiral ligands
5/20/2019
Hot Topics and Hypes

20. Chiral conversions
5/20/2019
Hot Topics and Hypes