Post on 12-Sep-2015
Katalis Homogen
Katalis
Jenis katalis
Katalis homogen adalah senyawa yang ada dalam fase yang sama (gas atau cair) sebagai reaktan,
sedangkan katalis heterogen
Organometallic
According to RSC
According to ACS
Noble-Prize Winners in Works Related to OM
Grignard & Saba
Trans Eect
In inorganic chemistry, the trans eect is the labiliza
ELECTRON COUNTING
Method 1: The ionic (charged) model
Pada metode ini melibatkan ligan sebagai pendonor pasangan electron ke logam. Untuk menentukan jumlah total electron, kita harus menghitung juga muatan se
Method 2: The covalent (neutral) model
Pada metode ini kita akan menggunakan jumlah electron yang akan didonasikan oleh ligand tetapi dalam keadaan netral. Pada ligan anorganik sederhana, jumlah electron yang didonasikan sama dengan muatan nega
Ligan dengan donasi elektronnya
TRANSITION METALS ORGANOMETALLICS
A transi:on metal is one which forms one or more stable ions which have incompletely
lled d orbitals.
Transition vs Main Elements The physical and chemical properties of transition metals differ from main group metals (s-block) by the following: are hard and have high densities. have high melting and boiling points. form compounds which are often paramagnetic. show variable oxidation states. form coloured ions and compounds. form compounds with profound catalytic activity. form stable complexes.
Transi:on Metals Overview
Early Transi:on Metals Groups 3, 4
Strongly electrophilic (Strongly bounds to high electronega
Early Transi:on Metals Groups 3,4
Typical catalysis in Polymerization
"Middle" Transi:on Metals Groups 5-7
Many accessible oxida
"Middle" Transi:on Metals Groups 5-7 Typical catalysis: Alkene and alkyne metathesis
Nomenclature
The mode of aRachment of the donor ligand is described by deno
Metal Carbonyls (Bonding)
Evidence of Back-bonding
Note that an empty orbital in the ligand (LUMO) is used in the bonding (an an
Metal Phosphines
Ter
Bonding in Metal Phosphines
Electronic Eects of Phosphines
Controlling The Space Around The Metal
Correla:on of Cone Angles & Reac:on
Mono-dentate Phosphines
Tolman plot of Electronic Parameter and Cone Angle
Hydrido Complexes
METAL AMINE
Metal Alkenes (Bonding)
Commonly used sources of Pd0 include:
Tris(dibenzylideneacetone)dipalladium (0) Pd2(dba)3
Tetrakis(triphenylphosphine)palladium (0)
Pd(PPh3)4
Also, Pd(II) is very readily reduced to Pd(0):
Thus, it is o`en more convenient to use Pd(II) complexes, which are more air-stable than commercial Pd(0) complexes.
Complex Rate Constant (s-1) T(oC)
PdCH3Ph3P
Ph3P CH3
PdCH3MePh2P
MePh2P CH3
PdCH3P
P CH3
PhPh
PhPh
1.04 x 10-3 60
60
80
9.62 x 10-5
4.78 x 10-7
Relative rates of reductive elimination
Most crowded is the fastest reaction
PdCH3L
L CH3+ solv
-L
PdCH3L
solv CH3
RELPd(solv) + CH3 CH3
SUZUKI-MIYAURA CROSS COUPLING REACTION
Bagaimana Mekanismenya??
MECHANISM OF SUZUKI-MIYAURA CROSS COUPLING REACTION
Selected examples of the Suzuki-Miyaura coupling in organic synthesis
I OR + ZnCl ORTHF, 60o C
[Pd(PPh3)2Cl2]
L = (PPh3)2
Predict the main products, include the mechanism
I +Pd-Cat
n-Bu3N, DMF
Br +THF, 60o C
Pd-Cat
O
O
O
O