1. Organometallic Chemistry an overview of structures and reactions Peter H.M. Budzelaar

2. Organometallic Chemistry 2 Between organic and inorganic... Organic chemistry: more or less covalent C-X bonds rigid element environments fixed oxidation states (better: valencies) ??Organometallic chemistry?? Inorganic chemistry: primarily ionic M-X bonds, dative M-L bonds variable and often fluxional environments variable oxidation states

3. Organometallic Chemistry 3 Organometallic reactivity Since most organometallics are intermediates, the focus in organometallic chemistry is usually on understanding and tuning reactivity This starts with analyzing reaction mechanisms in terms of elementary steps The number of possible elementary steps is larger than in "pure organic" chemistry, but the ideas are similar

4. Organometallic Chemistry 4 Organometallic structures Knowledge of inorganic and coordination chemistry is useful to understand geometries, electron counts and oxidation states of organometallic compounds Organometallics are more covalent and often less symmetric than coordination compounds, so orbital symmetry arguments are not as important

5. Organometallic Chemistry 5 Trends in organometallic chemistry Organometallic chemistry is concerned with all metals, in combination with all "organic" elements. there are many metals ! Generalization is important the chemistry of e.g. Fe is not much more complicated than that of C, but after that there are 80 more metals... we divide reactions in broader categories than organic chemists do We concentrate on the M side of the M-C bond, and on how to tune its reactivity

6. Organometallic Chemistry 6 Elements of interest Organic elements Main group metals Transition metals

7. Organometallic Chemistry 7 Organic vs organometallic reactivity Organic chemistry: C-C / C-H : nearly covalent C  + -X  - : polar (partly ionic) reactivity dominated by nucleophilic attack at C S N2 and S N1 like reactivity Organometallic chemistry: C is the negative end of the M-C bond ("umpolung") reactivity dominated by electrophilic attack at C or nucleophilic attack at M associative and dissociative substitution at M

8. Organometallic Chemistry 8 Main-group organometallics s and p orbitals. 8-e rule, usually. with a lot of exceptions More electropositive and larger: higher coordination numbers, regardless of the number of electrons. “Early" groups and not very electropositive: lower coordination numbers. 8-e 10-e 4-e

9. Organometallic Chemistry 9 Main-group organometallics Metal is the "  +" side of the M-C bond. Chemistry dominated by nucleophilic attack of C  - at electrophiles. this is also the main application in organic synthesis note: this is a simplified picture of the Grignard reaction

10. Organometallic Chemistry 10 Main-group organometallics M-M multiple bonds are fairly weak and rather reactive they are a curiosity and relatively unimportant, certainly compared to C-C multiple bonds Bond strengths in kcal/mol: C-C85C=C150 N-N40N=N100 P-P50P=P75 Multiple-bonded compounds often have unusual geometries

11. Organometallic Chemistry 11 Transition-metal organometallics s, p and d orbitals 18-e rule, sometimes 16-e other counts relatively rare 18-e 16-e

12. Organometallic Chemistry 12 Transition-metal organometallics Lower electron counts if metals are sterically saturated: 13-e 12-e note: actual structure is not octahedral ! 16-e

13. Organometallic Chemistry 13 Transition-metal organometallics Often ligands capable of donating 2-8 electrons Preference for  -system ligands (good overlap with d-orbitals) Bonding to neutral ligands (olefin/diene/CO/phosphine) relatively weak Important for catalysis!

14. Organometallic Chemistry 14 Transition-metal organometallics “Forbidden” reactions ?

15. Organometallic Chemistry 15 Reactivity of the M-C bond Polar  reactive towards e.g. Water: Me 3 Al explodes with water; Me 4 Sn does not react. Oxygen: Me 2 Zn inflames in air; Me 4 Ge does not react. Carbonyl groups: MeLi adds at -80°C, Me 3 Sb not even at +50°C.

16. Organometallic Chemistry 16 Reactivity of the M-C bond Oxidation and hydrolysis: large driving force Bond strengths in kcal/mol: Al-C65As-C55Si-C74 Al-O119As-O72Si-O108 Al-Cl100Si-Cl91

17. Organometallic Chemistry 17 Organometallic reaction steps Ligand dissociation / coordination note: free Me 3 Al dimerizes to Me 6 Al 2

18. Organometallic Chemistry 18 Organometallic reaction steps Insertion and  -elimination

19. Organometallic Chemistry 19 Organometallic reaction steps Insertion and  -elimination

20. Organometallic Chemistry 20 Organometallic reaction steps Oxidative addition / Reductive elimination

21. Organometallic Chemistry 21 Organometallic reaction steps Oxidative addition / Reductive elimination

22. Organometallic Chemistry 22 Organometallic reaction steps  -bond metathesis

23. Organometallic Chemistry 23 Organometallic reaction steps Redox reactions Homolysis

24. Organometallic Chemistry 24 Organometallic reaction steps Reactivity of coordinated ligands

25. Organometallic Chemistry 25 Factors governing structure and reactivity of organometallic compounds M-C, M-X bond strengths Electronegativity of M (polarity of M-C etc bonds) Number of (d) electrons Coordination number Steric hindrance

26. Organometallic Chemistry 26 Trends in the periodic table Main group metals: left and down: more electropositive down: higher oxidation states less stable Transition metals: middle: strongest preference for 18-e 2 nd and 3 rd row: strong preference for paired electrons (low-spin states) down: higher oxidation states more stable

27. Organometallic Chemistry 27 Working with organometallics Synthesis and reactivity studies (inert atmosphere!): Glove box Schlenk line, specialized glassware Characterization: Xray diffraction  structure  bonding NMR  structure en dynamic behaviour (calculations) IR MS EPR Not: GC LC