Chemistry 462 Fall 2016 MYD

Organometallic Chemistry and Applications Organometallic chemistry timeline

1760 Louis Claude Cadet de Gassicourt investigates inks based on cobalt salts and isolates cacodyl from cobalt mineral containing arsenic 1827 William Christopher Zeise produces Zeise's salt; the first platinum / olefin complex 1848 Edward Frankland discovers diethylzinc 1863 Charles Friedel and James Crafts prepare organochlorosilanes 1890 Ludwig Mond discovers nickel carbonyl 1899 Introduction of Grignard reaction 1899 John Ulric Nef discovers alkynation using sodium acetylides. 1900 Paul Sabatier works on hydrogenation organic compounds with metal catalysts. Hydrogenation of fats kicks off advances in food industry, see margarine 1909 Paul Ehrlich introduces Salvarsan for the treatment of syphilis, an early arsenic based organometallic compound 1912 Nobel Prize Victor Grignard and Paul Sabatier 1930 Henry Gilman works on lithium cuprates, see Gilman reagent 1951 Walter Hieber was awarded the Alfred Stock prize for his work with metal carbonyl chemistry.

1951 Ferrocene is discovered 1963 Nobel prize for Karl Ziegler and Giulio Natta on Ziegler-Natta catalyst 1965 Discovery of cyclobutadieneiron tricarbonyl 1968 Heck reaction 1973 Nobel prize Geoffrey Wilkinson and Ernst Otto Fischer on sandwich compounds 1981 Nobel prize Roald Hoffmann and Kenichi Fukui for creation of the Woodward-Hoffman Rules 2001 Nobel prize W. S. Knowles, R. Noyori and Karl Barry Sharpless for asymmetric hydrogenation 2005 Nobel prize Yves Chauvin, Robert Grubbs, and Richard Schrock on metal-catalyzed alkene metathesis 2010 Nobel prize Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for palladium catalyzed cross coupling reactions The following slides are meant merely as examples of the catalytic Processes we will explore later this semester. Please don’t get Disturbed that they are too much new information at this point. Believe me, you will see them again. Olefin hydroformylation Monsanto Acetic Acid Process

cross-coupling hydroformylation Olefin hydroformylation Hydroformylation—Cobalt Catalyst Monsanto Acetic Acid Process Cossee mechanism for olefin polymerization Acetyl co-A synthase

3+ Co1+-CoFeSP P CH3Co -CoFeSP P H + H S CH2 Ligand association C 2+/1+ 0 S 2+ [Fe4S4] Ni 2+/1+ Ni S N [Fe4S4] S N H3C 2+ 2+ M R M Ni Ni S N S N O O R O

1,2-insertion CoA

H3C S P CO P H - R H2C CoAS C R H M M 2+/1+ S S CO [Fe4 4] Migratory Insertion S 2+ 2+/1+ H C Ni [Fe4S4] 3 S N Ni2+ H C S N Ni2+ 3 Ni2+ S N O O S N O

ring-opening metathesis polymerization water-gas shift

CO OC Fe CO OC CO

O OH C OC Fe OC CO Fe CO OC OC CO CO

H H OC H Fe OC Fe OC CO CO OC CO CO CO reduction catalyst 2 Chauvin mechanism for olefin metathesis

P P H H CH Co3+-CoFeSP Co1+-CoFeSP CH2 + Ligand association C 3

S S 2+/1+ Ni0 2+ M R [Fe4S4] S N 2+/1+ S Ni M [Fe4 4] H C S N 2+ 3 Ni Ni2+ S N S N R O O

1,2-insertion CoA H3C S CO P - P CoAS H R H2C C 2+/1+ S S CO R [Fe4 4] Migratory Insertion S 2+ 2+/1+ H H C Ni [Fe4S4] 3 S N Ni2+ M H C S N Ni2+ 3 M Ni2+ S N O O S N O

Ref. : Christina White UCIU

Ref. : Christina White UCIU Ref. : Christina White UCIU

Ligands of Organometallic Chemistry. Homoleptic complexes from CO and PR3.

HOMO LUMO Tolman Electronic Parameter for Ligand Donor Ability Tolman electronic parameter Tolman steric parameter

5 Ferrocene: (η - C5H5)2Fe

mpt: 172°C; bpt: 250°C !! No decomposition.

https://www.youtube.com/watch?v=H6_E6C_e_fg 5 Ferrocene: (η - C5H5)2Fe

What symmetry element distinguishes the two?