Katalis

Homogen

Target capaian

Mengetahui apa itu katalis homogen.

Mengetahui denisi organologam
Mengetahui cara menghitung elektron
Mengetahui karakteris9k dari logam transisi
Mengetahui elektronik efek dan sterik efek dari ligan
Mengetahui cara menentukan arah jalan reaksi (asosiasi
atau disosiasi)
Mengetahui mechanis)c steps pada reaksi cross-coupling.
Aplikasi katalis homogen pada Suzuki, Negishi, dan Heck
Cross Coupling reac)on

Katalis

Jenis katalis
Katalis homogen adalah senyawa yang ada
dalam fase yang sama (gas atau cair) sebagai
reaktan,
sedangkan katalis heterogen 9dak berada
dalam fase yang sama dengan reaktan.

 Katalisis asam, katalis organologam, dan katalisis

enzima9k adalah contoh katalis homogen.
Paling sering, katalis homogen melibatkan
pengenalan katalis fase cair ke dalam larutan
reaktan.
Dalam kasus tersebut, asam dan basa sering
katalis sangat efek9f, karena mereka dapat
mempercepat reaksi dengan mempengaruhi
polarisasi ikatan.

Keuntungan dari katalis homogen adalah bahwa

katalis lebih cepat bercampur ke dalam
campuran reaksi, yang memungkinkan 9ngkat
yang sangat 9nggi dari interaksi antara molekul
katalis dan reaktan. Namun, berbeda dengan
katalisis heterogen, katalis homogen sering 9dak
bisa kembali ke bentuk awal ke9ka reaksi telah
berjalan sampai selesai.

Organometallic

According to RSC

According to ACS

Noble-Prize Winners in Works Related

to OM

Grignard & Saba9er (Grignard reagents) in 1912.

Ziegler & NaTa (Ziegler-NaTa catalyst) in 1963.
Fisher & Wilkinson (Sandwich complexes) in
1973.
Sharpless & Noyori (Hydrogena9on & Oxida9on)
in 2001.
Chauvin & Grubbs & Schrock (Alkene Meathesis)
in 2005.
Heck & Negishi & Suzuki (Pd catalyze C-C bond
forma9on) in 2010.

Trans Eect

In inorganic chemistry, the trans eect is the
labiliza9on (making unstable) of ligands that are
trans to certain other ligands, which can thus be
regarded as trans-direc9ng ligands. It is
aTributed to electronic eects and it is most
notable in square planar complexes, although it
can also be observed for octahedral complexes.
The cis eect is most oaen observed in
octahedral transi9on metal complexes.

ELECTRON COUNTING

Basis of Electron Coun9ng

Importance of Electron Coun9ng

Coun9ng Electron
Method 1: The ionic (charged) model
Method 2: The covalent (neutral) model

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 se9ap ligand dan menentukan
9ngkat atau bilangan oksidasi formal dari atom pusat.
Contoh: dikarbonil kloro pentahapto siklopentadienil besi (II) (5C5H5)Fe(CO)2Cl
5-C5H5- mendonorkan 3 pasang e-, CO mendonorkan 2 elektron
(karena terdapat 2 CO maka dikali 2), Fe(II) = [Ar]4s03d6 jadi
mendonorkan 6 elektron, sehingga jika dijumlahkan:
Fe (II) : 6 e-
5-C5H5 - : 6 e-
2(CO) : 4 e-
Cl- : 2 e-
Total eletron : 18 elektron

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 nega9fnya sebagai ion bebas.
Misalnya Cl donor 1 e- (muatan ion bebas -1), O donor 2 e- (muatan ion bebas -2),
N donor 3 e- (muatan ion bebas -3). Pada metode ini kita 9dak memerlukan
penentuan bilangan oksidasi dari atom pusat.
Contoh: dikarbonil kloro pentahapto siklopentadienil besi (II) (5-C5H5)Fe(CO)2Cl
Fe mendonorkan 8 e- sesuai kongurasi elektronnya, 5-C5H5 mendonorkan 5 e-
(kita memper9mbangan ligan ini sebagai ligan netral), CO mendonorkan 2 e-, dan
Cl mendonorkan 1 e- (sebagai spesies netral)
Fe : 8 e-
5-C5H5 : 5 e-
2(CO) : 4 e-
Cl : 1 e-
Total = 18 e-

Ligan dengan donasi elektronnya

La9han

Tugas

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
electronega9ve ligands that stablize higher oxida9on
states such as F-, O2-, =O).
Few redox reac9ons (excep9on: Ti)
Usually electron decient complexes (less than 18e).
Polar and very reac9ve M-C bonds (to alkyl and aryl).
Few d-electrons:
preference for "hard" -donors
weak complexa9on of -acceptors

Early Transi:on Metals Groups 3,4

Typical catalysis in Polymerization

"Middle" Transi:on Metals

Groups 5-7

Many accessible oxida9on states.

Mostly electron precise (18e).
Ligands strongly bound.
Strong, not very reac9ve M-C bonds.
Preference for -donor/-acceptor combina9ons
(such as CO and NO).

"Middle" Transi:on Metals Groups

5-7

Typical catalysis: Alkene and alkyne metathesis

Late Transi9on Metals Groups 8 (and

9)

Many accessible oxida9on states.

Mostly 18e or 16e (16e common for squareplanar complexes).
Easy ligand associa9on/dissocia9on
Weak, not very reac9ve M-C bonds (weak
orbitals overlap with low bond polarity).
Even weaker, reac9ve M-O/M-N bonds
Preference for s-donor/weak p-acceptor ligands
(phosphines)

Late Transi9on Metals Groups 8 (and 9)

Typical catalysis: C-C bond forma9on

Transi9on Metals

1st row:
oaen unpaired electrons (High spin state).
dierent spin states (HS/LS) accessible
highest oxida9on states not very stable
2nd/3rd row:
nearly always "closed shell"
Highest oxida9on states fairly stable
2nd row oaen more reac9ve than 3rd

Nomenclature

The mode of aTachment of the donor ligand is
described by deno9ng the number of atoms (together
with posi9ons if necessary) aTached to the metal atom
by n.
e.g. pentacarbonyl(1-methyl)manganese(I),
MnMe(CO)5
(1-allyl)pentacarbonylmanganese(I), Mn(1CH2CH=CH2)(CO)5
(3allyl)tetracarbonylmanganese(I), Mn(CO)4(3C3H5)
tricarbonyl(5-cyclopentadienyl)manganese(I),
Mn(CO)3(5-C5H5)

Metal Carbonyls (Bonding)

Evidence of Back-bonding

Note that an empty orbital in the ligand
(LUMO) is used in the bonding (an an9bonding orbital).
Using the an9-bonding orbitals in the ligand
decreases the strength of the bond (Bond
Order in MO theory).
Many techniques can read the weakness of
the ligand bonding (X-ray - IR NMR Mass
Spectrometry).

Metal Phosphines

Ter9ary phosphines, PR3, are important because
they cons9tute one of the few series of ligands in
which altera9on of electronic and steric
proper9es can be managed in a systema9c and
predictable way over a very wide range by
varying R groups.
Other eects can be introduced such as chelate
and macrocyclic eects. Also, chirality can be
introduced by having chiral phosphine ligands.
They also stabilize wide variety of ligands of
interest as their phosphine complexes (R3P)nML.

Bonding in Metal Phosphines

Electronic Eects of Phosphines

La9han
Pada senyawa kompleks [Mo(L)3(CO)3],
dengan membandingkan variasi L pada baris 4
dan 6

Jelaskan mengapa terjadi perbedaan nilai
energi peregangan / stretching pada CO?

QUIS
Pada senyawa kompleks [Mo(L)3(CO)3],
dengan membandingkan variasi L pada baris 6
dan 7

Jelaskan mengapa terjadi perbedaan nilai
energi peregangan / stretching pada CO?

Bonding in Metal Phosphines

Phosphine Donors

Lowest CO stretching
frequency:

most donating
phosphine

OC

O
C

C
O

Highest CO stretching
frequency:

least donating
phosphine
(best p -acceptor)

Phosphine Donor Ability Ranked by

Tolmans Electronic Parameter
(most donating to least)
PR3

mixed

P(OR)3

PX3

, cm1

PR3

mixed

PCy3

2056.4

PPh2(OPh)

2058.3

PPh2(C6F5)

2074.8

P(i-Pr)3

2059.2

P(O-i-Pr)3

PBu3

2060.3

P(OEt)3

PEt2Ph

2077.0

P(CH2CH2CN)3

2077.9
2079.3

PMe2Ph

2065.3

P(OMe)3

2079.5

PPh2(o-OMe-C6H4)

2066.1

P(o-Tol)3
PEtPh2
PMePh2
P(m-Tol)3
PPh2(NMe2)

2079.8
PPh2Cl

2066.6

PMe2CF3

2066.7

P(O-2,4-Me-C6H3)3

2067.0

P(OCH2CH2Cl)3

2084.0

2067.2

P(O-Tol)3

2084.1

2067.3

P(OPh)3

2085.3

2067.4

PPhBz2

2067.6

PPh2(p-OMe-C6H4)

2068.2

PPh3

PPh(OPh)2

2066.4

PPh2(2,4,6-Me-C6H2)

PPh2Bz

2080.7
2080.9
PH3

P(OCH2)3CR

2083.2

2086.8

P(OCH2CH2CN)3

2087.6

P(C6F5)3

2090.9

2068.4
2068.9

PCl3

2097.0

PF3

2110.8

2069.3

PPh(OEt)2

2074.2

PPh2(p-F-C6H4)

2069.5

PPh2(OPh)

2074.6

PPh(p-F-C6H4)2

2070.0

PPh2(C6F5)

PPh2(CH=CH2)
P(CH=CH2)3

2076.3

P(OCH2CH2OMe)3

PBz3
P(p-Tol)3

2063.7

2075.9

2064.1

PMe3
P(p-OMe-C6H4)3

PPhH2

2061.7

, cm1
2074.6

2056.1

PEt3

PX3

2074.2

P(t-Bu)3
P(o-OMe-C6H4)3

P(OR)3

PPh(OEt)2

2074.8

2071.3

P(O-i-Pr)3

2075.9

PPh2(OEt)

2071.6

P(OEt)3

2076.3

PPh2(OMe)

2072.0

P(p-F-C6H4)3

PPh(O-i-Pr)2
P(p-Cl-C6H4)3
PPh2H

2072.2

PPhH2

2077.0

P(CH2CH2CN)3

2077.9

2072.8

P(OCH2CH2OMe)3

2079.3

2073.3

P(OMe)3

2079.5

La9han
Order the following phosphines from
strongest to weakest donor:
P(OEt)3, PPh3, PPr3, PCl3, PPh2(OMe)

KUIS
Order the following phosphines from best acceptor to worst -acceptor:
P(OEt)3, PPh3, PPr3, PCl3, PPhCy2

Tolmans Cone Angle

The size or steric bulk of a phosphine ligand was determined from
simple 3-D space-lling models of the phosphine ligands. Tolman
coined the name cone angle (q) to indicate the approximate amount
of space that the ligand consumed about the metal center.

cone angle q

Controlling The Space Around

The Metal

Correla:on of Cone Angles &

Reac:on

PR3

mixed

P(OR)3

PX3

()

P(i-Pr)3

160

PBz3

165

PCy3

PPh(t-Bu)2

170
P(O-t-Bu)3

P(t-Bu)3

175
182

P(C6F5)3

184

P(o-Tol)3

194

P(mesityl)3

212

Order the following phosphines from smallest

to largest:
P(OEt)3, PPh3, PPr3, PCl3, PPhCy2

Mono-dentate Phosphines

 We can increase the bulkness around the

metal by replacing the phosphine ligand
without aec9ng the electronic factor
PMe3 (1180) and PEt2Ph (1330)
We can change the electronic factor around
the metal by replacing the phosphine ligand
without aec9ng the bulkness.
P(C6H4-4-CH3)3, PPh3, P(C6H4-4-CN)3 (1450)

Tolman plot of Electronic Parameter

and Cone Angle

Hydrido Complexes

METAL AMINE

Metal Alkenes (Bonding)

Ligand Assosia9on & Dissocia9on

Dissocia9ve Sub9tu9on Mechanism

Commonly observed mechanis9c steps in

organometallic chemistry include:

Oxida9ve Addi9on
Reduc9ve Elimina9on
Transmetalla9on
Ligand Subs9tu9on
Coordina9on
Inser9on
-Hydride Elimina9on

An Example of an Oxida9ve Addi9on with a Non-transi9on Metal is the Grignard

Reac9on (Magnesium is an alkaline earth metal).

Oxida9ve addi9on of Pd
1) Oxida9ve Addi9on of Pd to C-X

Notes:
a) The oxida9ve addi9on step increases the oxida9on state of the metal by 2.
b) Therefore, it occurs most readily with electron rich metals and when the metal is
in a rela9vely low oxida9on state (e.g. Pd(0)). It cannot occur when the metal is
already at its highest oxida9on level.
c) The reac9on proceeds most readily when the carbon is sp2 hybridized (i.e. an aryl
halide, or a vinyl halide).

Commonly used sources of Pd0 include:

Tetrakis(triphenylphosphine)palladium
(0)
Pd(PPh3)4

Tris(dibenzylideneacetone)dipalladium (0)
Pd2(dba)3

Also, Pd(II) is very readily reduced to Pd(0):

Thus, it is oaen more convenient to use Pd(II) complexes, which are more
air-stable than commercial Pd(0) complexes.

2) Reduc9ve Elimina9on

Notes:
a) This reac9on is the reverse of oxida9ve addi9on
b) Therefore, the formal oxida9on state of the metal decreases by 2.

Relative rates of reductive elimination

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Rate Constant (s-1)

Complex
Ph3P

Pd

Ph3P

CH3

MePh2P
MePh2P
Ph

Ph
Pd

Ph

CH3

Ph

Pd

CH3
CH3

CH3
CH3

T(oC)

1.04 x 10-3

60

9.62 x 10-5

60

4.78 x 10-7

80

Most crowded is the fastest reaction

Transmetalla9on

Now we will put the three reac9ons together (oxida9ve

addi9on, transmetalla9on, and reduc9ve elimina9on) to
produce some very widely u9lized processes which
employ palladium (as Pd(0)) as a catalyst.

SUZUKI-MIYAURA CROSS COUPLING REACTION

Bagaimana Mekanismenya??

MECHANISM OF SUZUKI-MIYAURA CROSS COUPLING REACTION

TUGAS
OH

+ Et2N
Br

LnPd(0)

B
OH

Base, Solvent

Selected examples of the Suzuki-Miyaura coupling in organic synthesis

NOTED
When a reac9on is catalyzed by Pd(0), the mechanism for how it is produced
from a Pd(II) precursor is oaen not discussed, and in some cases may not
even be known. In the Suzuki reac9on, one way that Pd(0) can be generated
is by homocoupling the boronic acid precursor:

Because only a 9ny amount of Pd(0) is required to catalyze

the reac9on, a negligible amount of boronic acid is wasted,
and only minor amounts of the homocoupling product are
formed.

Negishi Cross-Coupling Reac9on

[Pd(PPh3)2Cl2]
I

OR +

ZnCl

OR

THF,

L = (PPh3)2

60o

HOMEWORK
Predict the main products, include the mechanism

To understand the Heck Reac9on, two

new processes will be introduced:

The inser9on reac9on

The -hydride elimina9on
Inser9on

-hydride elimina9on

The inser9on reac9on

Inser9on

The -hydride Elimina9on

-hydride elimina9on

Note that in order to have a -hydride elimina:on you MUST have an empty
orbital on the metal cis (next) to the alkyl ligand. You also must have hydrogens present on the alkyl.

 Avoid -hydride elimina9on

In order to prepare stable M-alkyl complexes

one, therefore, oaen needs to stay away from
alkyls with - hydrogens (or avoid metals with
empty coordina9on sites). Some common
ligands used to avoid -hydride elimina9on
reac9ons are shown below.

Would a 16 e- M-(t-butyl) complex be stable or not? Why?

Heck Reac9on

Pd-Cat
I +

n-Bu3N, DMF

O
Br

Pd-Cat

THF, 60o C

 The Heck reac9on is named aaer Professor Emeritus Richard

Heck of the University of Delaware. It is some9mes referred to
as the Mizoroki-Heck reac9on, to recognize the early
contribu9ons of the late Tsutomu Mizoroki , a professor at the
Tokyo Ins9tute of Technology . In recogni9on of Prof. Hecks
contribu9on to the eld of organopalladium chemistry, he was
awarded the Nobel prize in Chemistry in 2010, along with Akira
Suzuki (Hokkaido University) and Ei-ichi Negishi (Purdue
University) for their eponymous palladium-catalyzed cross
coupling reac9ons.

S:ll Cross-coupling Reac:on

X

nBu
+ R

Sn

Pd (0)

nBu

nBu
(c)
Reductive Elimination
Ar-Ar'

L
L

Pd

(a)
Oxidative Addition
Ar-X
X = I, Br, Cl

L2-Pd0

Ar
,

Ar

PdII
L

Ar

Ar
Pd
PdII L
Ar'-SnHBu3

Pd
Ar'

PdII

X-SnBu3
(b)
Transmetalation

Buchwald Hartwig cross-coupling reac:on

La9han

The Sonogashira coupling

The Hiyama Coupling

The Kumada Coupling

Summary