1. 6/11/2015Hot Topics and Hypes1 Hot Topics en Hypes in organometallic chemistry

2. 6/11/2015Hot Topics and Hypes2 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

3. 6/11/2015Hot Topics and Hypes3 Hypes Everything "BIO" and "NANO" Buckyballs, buckytubes Supramolecular chemistry Materials

4. 6/11/2015Hot Topics and Hypes4 C-H activation Problems: C-H bond is least reactive bond Product is usually more reactive than starting material  further oxidation Product is always better donor than starting material  product inhibition

5. 6/11/2015Hot Topics and Hypes5 C-H activation This will not work:

6. 6/11/2015Hot Topics and Hypes6 C-H activation This does work: B-B bond weak B-H and B-C strong product hardly coordinating

7. 6/11/2015Hot Topics and Hypes7 C-H activation A real example: Electrophilic attack on C-H bond (?)

8. 6/11/2015Hot Topics and Hypes8 CH 4 to CH 3 OH: how does industry do it? "hot pipes"

9. 6/11/2015Hot Topics and Hypes9 CH 4 to CH 3 OH: how does nature do it? (we think) MMO = "methane mono-oxygenase"

10. 6/11/2015Hot Topics and Hypes10 C-H activation C-H activation for CH 4  CH 3 OH 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

11. 6/11/2015Hot Topics and Hypes11 How can you study C-H activation? "microscopic reversibility" activation of more reactive C-H bonds e.g. aromatic C sp2 -H bonds

12. 6/11/2015Hot Topics and Hypes12 Selective oxidation Epoxidation: does not work for other olefins (allylic C-H bonds are too reactive)

13. 6/11/2015Hot Topics and Hypes13 Selective oxidation Aldehydes / ketones:

14. 6/11/2015Hot Topics and Hypes14 Selective oxidation Desired: Current process: hydroformylation

15. 6/11/2015Hot Topics and Hypes15 Anti-Markovnikov water addition Desired: Current process: via hydroformylation

16. 6/11/2015Hot Topics and Hypes16 Anti-Markovnikov water addition A possible organometallic route:

17. 6/11/2015Hot Topics and Hypes17 (Co)polymerization of functionalized olefins Desired: Problem:

18. 6/11/2015Hot Topics and Hypes18 (Co)polymerisation of functionalized olefins Possible solutions: Late transition metal complexes b.v. Ni/Pd Brookhart Protection of functional group Functionalization after polymerization

19. 6/11/2015Hot Topics and Hypes19 Chiral conversions Noyori / Knowles / Sharpless Precise tuning needed for every new reaction combinatorial catalysis? Few general principles Many "standard" chiral ligands

20. 6/11/2015Hot Topics and Hypes20 Chiral conversions