2. Transition metal organometallic compounds & Catalysis Metal-carbon bond: a few from many? Which one is organometallic? Ni(CO) 4 or NaCN ? French ChemistL. C. Cadet1760As 2 Me 4 dicacodyl

3. Ligand NameBonding Type Molecular Hydrogen: H 2 Hydride H - M-H Phosphine: PR 3 M-PR3M-PR3 Carbonyl: C  O Alkyl, ArylM-CR M-Ph Alkene Organometallic Compound: Looking closer

4. 18 en rule Organic compounds – Octet rule Organometallic – 18 electron rule * 18 valance electron – inert gas configuration 1920British ChemistSidgwick

6. To determine the electron count for a metal complex: Determine the oxidation state of the transition metal center(s) and the metal centers resulting d-electron count. To do this one must: a) note any overall charge on the metal complex b) know the charges of the ligands bound to the metal center c) know the number of electrons being donated to the metal center from each ligand 2)Add up the electron counts for the metal center and ligands Counting the number of electrons

7. Ligand NameBonding TypeFormal Charge Electrons donated Molecular Hydrogen: H 2 02 Hydride H - M-H2 Halide X - M-X2 Amine, phosphine, arsine: NR 3, PR 3, AsR 3 M-NR3 M-PR302 Carbonyl: C  O 02 Alkyl, ArylM-CR M-Ph2 Alkene2 Counting the number of electrons

10. Catalysis A + B C CatalystHeterogeneousHomogeneous A catalyst lowers the activation barrier for a transformation, by introducing a new reaction pathway. It does not change the thermodynamics!!

11. Synthesis of chemicals… pharmaceutical, agricultural Catalytic converter … environmental Biological system – efficient catalyst Catalysis : Why? Organometallic compounds, metals etc.

12. How to select an efficient catalyst? Activity: related to rate of reaction (also called turnover) efficient catalyst: good activity Turnover frequency (N) N = /[Q] Large turnover frequency – efficient catalyst Selectivity: Byproducts should be minimized Lifetime: It is costly to replace the catalyst frequently Cost: The acceptable cost depends upon the catalyst lifetime, product value lifetime and product value Poisoning: decomposition of catalyst, adsorption of reactant/product

13. Coordination compounds in catalysis Nobel Prizes 2005 Yves Chauvin,Robert H. Grubbs and Richard R. Schrock. 2001KNOWLES, NOYORI, SHARPLESS 1973WILKINSON 1963ZIEGLER, NATTA 1918HABER 1909OSTWALD

14. Hydrogenation of Unsaturated Hydrocarbons The most common catalyst  Wilkinson’s Catalyst, [RhCl(PPh 3 ) 3 ] -CH=CH- + H 2  -CH-CH- HH NOBEL : 2001

15. Wilkinson’s Catalyst (WC) Chlorotris(triphenylphosphine)rhodium(I) square planar d 8 configuration

16. Geoffrey Wilkinson Born July 14, 1921, Yorkshire, England Ph.D from Cal Berkeley studying with Glenn Seaborg First published compound in 1965 in Journal of the Chemical Society - Chemical Communications Nobel Prize in Chemistry 1973 (shared with Ernst Otto Fischer) for their pioneering work, performed independently, on the chemistry of the organometallic, so called sandwich compounds. Organometallic compounds prepared by Wilkinson in display at Harvard Univ.

17. Synthesis of WC Commercially available

18. Catalytic steps (a) Ligand coordination and dissociation Facile coordination of the reactant and facile loss of products. Coordinatively unsaturated - 16-electron complexes (b) Oxidative addition Metal must possess a non-bonding electron pair Coordinatively unsaturated Oxidation of metal by two units – M n to M n+2 -occurs when a complex behaves simultaneously as a Lewis base and a Lewis acid

19. Oxidative addition…

20. (c) Insertion or migration Migration of alkyl and hydride ligands

22. (d) Nucleophilic attack

23. (d) Reductive elimination Involves decrease in the oxidation and coordination number

24. Hydrogenation of Unsaturated Hydrocarbons -CH=CH- + H 2  -CH-CH- HH  G 0 = -101 kJ/mol

25. Rh +1 Rh 3+ (1) Oxidative addition (2) Ligand Dissociation WC in alkene Hydrogenation: Catalytic Steps

26. (3) Ligand Association (4) Migration/Insertion WC in alkene Hydrogenation: Catalytic Steps

27. (5) Ligand association WC in alkene Hydrogenation: Catalytic Steps

28. (6) Reductive elimination WC in alkene Hydrogenation: Catalytic Steps

29. WC IN A C T I O N

30. Rate of the reaction decreases as the alkyl substitution increases Highly sensitive to the nature of the phosphine ligand Analogous complexes with alkylphosphine ligands are inactive Highly selective for C=C over C=O WC in alkene Hydrogenation: Additional Notes * Laboratory scale organic synthesis * Production of fine chemicals Applications

31. Chiral phosphine ligands have been developed to synthesize optically active products. Synthesis of L-DOPA (Used in the treatment of Parkinson’s diseases) Synthetic route was developed by Knowles & co-workers at Monsanto Dr. William S. Knowles received Nobel prize in chemistry 2001 along with other two scientists. Alkene Hydrogenation & Chirality & Nobel

32. This reaction, developed by Knowles, Vineyard, and Sabacky, was used at Monsanto as a commercial route to the Parkinson's drug L-DOPA. Alkene Hydrogenation, Chirality & Nobel

34. Non-superimposable mirror image Enantiomeric excess = (moles of major enantiomer - moles of other enantiomer / Total moles of both enantiomers) 100

35. phenylanisylmethylphosphine (PAMP) Dimeric product is DiPAMP

37. Additional notes For interested students (a) Ligand coordination and dissociation Facile coordination of the reactant and facile loss of products. Coordinatively unsaturated - 16-electron complexes (b) Oxidative addition Metal must possess a non-bonding electron pair Coordinatively unsaturated Oxidation of metal by two units – M n to M n+2 -occurs when a complex behaves simultaneously as a Lewis base and a Lewis acid

38. Oxidative addition…

39. (c) Insertion or migration Migration of alkyl and hydride ligands

41. (d) Nucleophilic attack

42. (e) Reductive elimination Involves decrease in the oxidation and coordination number