Organometallic Chemistry

Dr. rar. nat. Agustino Zulys M.Sc.

Organometallic Chemistry
Instructor : Dr. rer. nat. Agustino Zulys M.Sc. Class Schedule: Tuesday, 17:00 Text Book:
Organometallics a concise introduction Ch. Elschenbroich, A. Salzer, VCH, Weinhein Application of Organometallic Compounds, Iwao Omae, Wiley and Sons Ltd, Chichester

Attendance 80% Examination

Presentation 40% Final Test 60%

Class Schedule
Pendahuluan Struktur dan ikatan Tipe-tipe ligand, bilangan oxidasi logam dan aturan 18 elektron Reaktifitas organometallic Organometallic Catalysis

Pendahuluan
INORGANIC CHEMISTRY

Organometallic

Catalysis

ORGANIC CHEMISTRY

PHYSICAL CHEMISTRY

Pendahuluan
Definisi : Senyawa-senyawa yang memiliki ikatan M-C yang terbentuk dari sebuah atom logam dengan atom carbon (C). M+ CC-, M+ CN- bukan Organometallic (kompleks Anorganik). M-H, M-N2 senyawa organometallic (Td rendah, ikatan M-C less polar). Senyawa Anorganik : metals, ores and senyawasenyawa yang memiliki sifat ikatan ionic. Eq Metal-like carbides: (e.g. WC, TiC, TaC), diamond like carbides: (ZrC,VC, HfC, SiC), salt-like carbides: (CaC2, Be2C) Senyawa OM sangat labile, kereaktifitasan tinggi, selektifitas produk tinggi

Pendahuluan

Pendahuluan

N C

Na Fe OC CO
C N NC NC

CO
CN

Fe

CN

Ni OC

CO CO

Hystory Organometallic Compounds

1760 cadets fuming arsenical liquid
heat 2CH3COOK (CH3)2C=O heat (CH3)2C=O 2CH3 + + K2CO3 CO

CO As2O3 [As] -CO2

CH3

Me2As-AsMe2 Me3As

(cacodyl)

Me2AsAs(Me)AsMe2

(MeAs) 5 Me7As3 CH3COOH

(Me2As) 2O

cacodyl oxide

Hystory Organometallic Compounds

1827 Zeises Salt Na[PtCl3C2H4]
PtCl 2 + PtCl4 + C2H5OH heat alcohol distilled of f aq KCl [PtCl3.C2H4] -

1868 by Birnbaum
Cl Cl

H2PtCl6

C2H4

[PtCl3.C2H4

]-

Pt Cl

Hystory Organometallic Compounds

1849 Frankland, Zn(Et)2, first metal alkyl EtI + Zn EtZnI 2EtZnI Et2Zn + ZnI2 1900 Grignard, organomagnesium halides
Saytzeff methode
O

Zn MeI
R1 R2 R1

OZnI Me R2

OH

H2O
R1

Me R2

Barbier methode
O

Mg MeI

OMgI

OH

H 2O

Hystory Organometallic Compounds

1909 Pope and Peachey, PtMe3I, first transition metal s-alkyl 1917 Schenk, lithium alkyls 1931 Heiber, Fe(CO)4H2 first transition metal hydride 1951 Pauson and Miller, ferrocene, Fisher, bis arene metal complex 1972 Total Syntheses of Vit B12 1973 Fisher, Cr(CO)4(CR), first carbyne complex 1983 Bergman, Graham, C-H bond activation 1983 Green, Brookhart, agostic metal-hydrogen interaction 1985 the discovery of fullerene

Application Of Organometallic Compounds

Organosynthetic Reagents Isolation of pure metal or its metallic compound. Generally difficulte to produce pure metal from ores.
By thermal decomposition of metal carbonyls Fe(CO)5 or Ni(CO)4 the pure metallic iron and nickel are available. By decomposition with light, a plasma and electron beam

Highest toxicity of organo group 14 element and Hg, As Pb for germicides, insecticides, pharmaceuticals and agricultural chemicals Organometallic high polymer Homogeneous Catalysis

MOCVD (Metal-Organic Chemical Vapor Deposition) or OMVPE (Organometallic Vapor Phase Epitaxy) e.g Me3Al, Cr(CO)6, (6C6H6)2Cr, Cp2Co, CpCuPEt3, Fe(CO)5, Et4Pb, Mn2(CO)10, Ni(CO4), Cp2Ni, (h3C3H5)2Pd, Me4Sn, (neopentyl)4Ti and Me2Zn. semiconductor elements, elecroconductive materials, magnetic materials, hard materials, heatresistent materials and superconductive materials. For example, SnO2 (a transparent electroconductive material) is produced by thermal decomposition of Me4Sn with O2. TiC (a hard material) by thermal decomposition of (neopentyl)4Ti

Aspects of Organometallic
Main Group Metals : s, p orbitals, 8 electron rules Transition Metal : s, p and d orbitals, 18 electron rules Lanthanide Metals: s, orbital, electrostatic attraction Types of Ligand, , , , , Reactivity of organometallic
Substitution Oxidative addition Reductive elimination Metallation, Transmetallation Direct synthesis Insertion, elimination etc

Characterization of Organometallic Chemistry

Xray diffraction structure bonding NMR structure and dynamic behaviour (calculations) IR MS EPR Not : GC, LC, HPLC