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Homogen
Target capaian
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.
Organometallic
According to RSC
According to ACS
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
Coun9ng Electron
Method 1: The ionic (charged) model
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-
La9han
Tugas
TRANSITION METALS
ORGANOMETALLICS
A transi:on metal is one which forms one or more stable ions which have incompletely
lled d orbitals.
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)
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.
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?
Phosphine Donors
Lowest CO stretching
frequency:
most donating
phosphine
OC
O
C
C
O
Highest CO stretching
frequency:
least donating
phosphine
(best p -acceptor)
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
cone angle q
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
Mono-dentate Phosphines
Hydrido Complexes
METAL AMINE
Oxida9ve Addi9on
Reduc9ve Elimina9on
Transmetalla9on
Ligand Subs9tu9on
Coordina9on
Inser9on
-Hydride Elimina9on
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).
Tetrakis(triphenylphosphine)palladium
(0)
Pd(PPh3)4
Tris(dibenzylideneacetone)dipalladium (0)
Pd2(dba)3
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.
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
Transmetalla9on
Bagaimana Mekanismenya??
TUGAS
OH
+ Et2N
Br
LnPd(0)
B
OH
Base, Solvent
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:
[Pd(PPh3)2Cl2]
I
OR +
ZnCl
OR
THF,
L = (PPh3)2
60o
HOMEWORK
Predict the main products, include the mechanism
-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.
Heck Reac9on
Pd-Cat
I +
n-Bu3N, DMF
O
Br
Pd-Cat
THF, 60o C
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
La9han
Summary