Mekanisme Reaksi Kimia Anorganik

Reaksi Organologam

Referensi:
James E.Huheey, Ellen A.Keither, Richard L. Keiter. 1993. Inorganic
Chemistry: Principles of Structure and Reactivity Fourth Edition. Harper
Collins College, New York (Bab 13, 15)
Miessler, Tarr, Inorganic Chemistry, 2nd Edition, 1999.
Shriver, Atkins, Inorganic Chemistry, 3rd Edition, 1999.
RH Crabtree, The Organometallic Chemistry of the Transition Metals, Wiley
2001
Online : http://www.chem.ox.ac.uk/icl/dermot.html
Lecture Notes online: www.ocw.mit.edu
Lecture Note yang telah dibagikan (Mencakup 2/3 materi, bahasa
Indonesia)
Help : ruang dosen, e-mail, phone
Pertemuan I- tugas terstruktur

 Kimia Organologam
Definisi Kimia Organologam
Aturan 18 elektron: Electron Counting (pertemuan I)
Ligan Organometal (pertemuan II)
Reaksi Kompleks Organologam (pertemuan III-V)
Adisi Oksidatif
Eliminasi Reduktif
Proses Substitusi
Reaksi Insersi
Eliminasi Alfa-Hidrida dan Abstraksi
Eliminasi Beta-Hidrida

Aplikasi dalam reaksi katalitik (pertemuan 5-7)

(Dengan Luasnya Kajian Kimia Organologam-hanya ada 7 pertemuan,
Bahasan per minggu dan slide power point dapat sedikit berubah
dari rencana pembelajaran)

Mekanisme Reaksi Kimia Anorganik

Reaksi Organologam

Organometallic compounds are compounds wherein the metal is bonded through

carbon to an organic molecule, radical or ion.

senyawaan yang mengandung ikatan LOGAM KARBON

Dari yang telah anda pelajari:Cr(CO)6
Hingga: senyawa sandwich dengan sistem ligan organik tak jenuh pi terdelokalisasi

BASED ON ORGANOMETALLICS JOURNAL:

"organometallic" compound will be defined as one in which
there is a bonding interaction (ionic or covalent, localized or
delocalized) between one or more carbon atoms of an organic
group or molecule and a main group, transition, lanthanide, or
actinide metal atom (or atoms).
organic derivatives of the metalloids (boron, silicon,
germanium, arsenic, and tellurium) will be included in this
definition.
metal-containing compounds which do not contain metalcarbon bonds will be considered as well. Such compounds
may include, inter alia, representatives from the following
classes: molecular metal hydrides; metal alkoxides, thiolates,
amides, and phosphides; metal complexes containing organogroup 15 and 16 ligands; metal nitrosyls...."

Historical Perspective
1827 Zeises Salt Na[PtCl3C2H4]-seny org.logam pertama
1847 Frankland, Zn(Et)2, first metal alkyl
1900 Grignard, organomagnesium halides
1907 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
1955 Fisher, bis arene metal complex
1973. Fisher, Cr(CO)4(CR), first carbyne complex
1983. Bergman, Graham, C-H bond activation
1983 Green, Brookhart, agostic metal-hydrogen interaction

The Nobel Prize in Chemistry 2010

Richard F. Heck, Ei-ichi Negishi, Akira Suzuki

Richard
F. Heck
American
citizen.
Born
1931

Ei-ichi
Negishi
Japanese
citizen.
Born
1935

Akira
Suzuki
Japanese
citizen.
Born
1930

Why the Heck Bother with the Heck Reaction:

Applications in Industry and Total Synthesis
Sunscreen Agents
Flavourings
Cosmetic Additives

COOH

O
O
MeO

Key Steps in Total Synthesis

Non-Steroidal
O
Anti-inflammatory drugs
Taxol
CH3
B
C
Skeleton
A
MeO

O
O
J.J. Masters, D.K. Jung,
W.G. Bornmann and
S.J. Danishefsky,
Tetrahedron Lett., 1993, 34, 7253

(s)-Naproxen

2-Ethylhexyl
trans-4-methoxycinnamate
O

O
MeO

MeO
Heck reaction
Br

Isoamyl
trans-4-methoxycinnamate

CC-1065
Skeleton

N
H
O

MeO

SO2Ph

L.F. Tietze and T. Grote,

J. Org. Chem., 1994, 59, 192

The Nobel Prize in Chemistry 2010

The Suzuki reaction

Suzuki reaction to
develop organic
polymers that emit
light when a current
runs through them.
The goal is to
improve super-thin
OLED (organic lightemitting diode)
displays.

Suzuki reaction to
develop new lightcapturing
molecules. These
can be spraypainted onto a
surface and could
become a part of
future flat solar cell

The Suzuki reaction

has been used to
develop variants of the
antibiotic vancomycin.
These variants are
effective against
strains of bacteria that
are otherwise resistant
(MRSA)

Ligan Organik tidak jenuh

Dapat berikatan dengan logam melalui lebih dari 1 cara
Contoh
Allyl
* Sbg alkil berikatan dgn logam melalui satu atom karbon
* melalui sistem elektron , ketiga atom karbonnya
berikatan dengan logam (hapticity, h)

M
12

Hapto (h) Number

Jumlah atom terkonjugasi pada ligan yang terikat ke logam
h5-C5H5 pentahaptosiklopentadienil
Sebagai ligan C5H5 disebut siklopentadienil (Cp)

13

x
h

eta-x was originally developed to indicate how many contiguous donor

atoms of a -system were coordinated to a metal center. Hapticity is another word
used to describe the bonding mode of a ligand to a metal center. An h5cyclopentadienyl ligand, for example, has all five carbons of the ring bonding to the
transition metal center.
hx values for all-carbon based ligands where the x value is odd usually
indicate anionic carbon ligands (e.g., h5-Cp, h1-CH3, h1-allyl or h3-allyl, h1CH=CH2). The # of electrons donated (ionic method of electron counting) by the
ligand is usually equal to x + 1. Even hx values usually indicate neutral carbon system ligands (e.g., h6-C6H6, h2-CH2=CH2, h4-butadiene, h4-cyclooctadiene).
The # of electrons donated by the ligand in the even (neutral) case is usually just
equal to x.

14

15

17

mx

mu-x is the nomenclature used to indicate the presence of a bridging

ligand between two or more metal centers. The x refers to the number of metal
centers being bridged by the ligand. Usually most authors omit x = 2 and just use

m to indicate that the ligand is bridging the simplest case of two metals.
There are two different general classes of bridging ligands:
1) Single atom bridges
2) Two donor atoms separated by a bridging group (typically organic)

Ta2 (m-t-Bu-CC-t-Bu) (m-Cl)2Cl2(THF)2

Mo2(m-CH2P(Me)2CH2)4

Ordering

Inorganic/organometallic chemists generally do NOT use

IUPAC naming rules.
There are some qualitative rules that most authors seem to use in American
Chemical Society (ACS) publications:
in formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes first,
followed by the metal center: Cp2TiCl2
other anionic multi-electron donating ligands are also often listed in front of
the metal, e.g., trispyrazolylborate anion (Tp)
in formulas with hydride ligands, the hydride is sometimes listed first. Rules #
1 & 2, however, take precedence over this rule: HRh(CO)(PPh3)2 and
Cp2TiH2
bridging ligands are usually placed next to the metals in question, then
followed by the other ligands (note that rules 1 & 2 take precedence):
Co2(m-CO)2(CO)6 , Rh2(m-Cl)2(CO)4 , Cp2Fe2(m-CO)2(CO)2
anionic ligands are often listed before neutral ligands: RhCl(PPh3)3,
CpRuCl(=CHCO2Et)(PPh3) (neutral carbene ligand), PtIMe2(CCR)(bipy).

Ordering

Inorganic/organometallic chemists generally do NOT use

IUPAC naming rules.
There are some qualitative rules that most authors seem to use in American
Chemical Society (ACS) publications:
in formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes first,
followed by the metal center: Cp2TiCl2
other anionic multi-electron donating ligands are also often listed in front of
the metal, e.g., trispyrazolylborate anion (Tp)
in formulas with hydride ligands, the hydride is sometimes listed first. Rules #
1 & 2, however, take precedence over this rule: HRh(CO)(PPh3)2 and
Cp2TiH2
bridging ligands are usually placed next to the metals in question, then
followed by the other ligands (note that rules 1 & 2 take precedence):
Co2(m-CO)2(CO)6 , Rh2(m-Cl)2(CO)4 , Cp2Fe2(m-CO)2(CO)2
anionic ligands are often listed before neutral ligands: RhCl(PPh3)3,
CpRuCl(=CHCO2Et)(PPh3) (neutral carbene ligand), PtIMe2(CCR)(bipy).

Problem: Sketch structures for the following:

a) CpRuCl(=CHCO2Et)(PPh3)

b) Co2(m-CO)2(CO)6 (Co-Co bond, several possible structures)

c) trans-HRh(CO)(PPh3)2 [Rh(+1) = d8]

d) Ir2(m-Cl)2(CO)4

e) Cp2TiCl2

[Ir(+1) = d8]

Aturan 18 elektron

Mirip dengan aturan Oktet, analogi s2p6d10

Sering dilanggar
Berguna untuk penghitungan dan perkiraan reaktivitas
Terdapat dua cara: ionik dan kovalen
Yang harus diketahui : muatan formal, d electron count

Metode ionik: menghilangkan ligan daril ogam dan jika perlu menambah elektron ke
tiap ligan adar terbentuk kulit valensi tertutup (closed valence shell).
Contoh jika kompleks memenuhi oktet, mengambil NH3 berarti mengambil NH3gugus metil sebagai 2 elektron donor., berhubung logam bermuatan positif maka
nantinya d-electron countnya harus dikurangi satu. Lihat contoh

Metode kovalen: menghilangkan seluruh ligan dalam bentuk netral. Misal amonia
dihilangkan sebagai molekul netral dengan sepasang elektron bebas. Mana amonia
adalah 2 elektron donor netral. Jika ligannya NH3 maka yang diambil berbentuk NH3
radikal, sebagai satu donor elektron, kemana yang satunya pergi? Dihitung pada
logam, kedudukan logam dihitung sebagai d-electron terisi penuh, misal Fe selalu 8.

23

24

25

26

27

ATURAN 18 ELEKTRON, WHY?

Contoh Cr(CO)6. interaksi d orbital Cr Ligan CO merupakan ligan sdonor (HOMO) dan -akseptor (LUMO)

28

 Penambahan 1 elektron akan memberikan populasi pada orbital egantibonding-destabilisasi

Pengurangan 1 el akan mengurangi t2g (bonding karena pengaruh
CO sebagai - akseptor )-destabilisasi, maka 18e paling stabil
Sifat s-donor CO meninggikan energi eg
Sifat - akseptor CO menurunkan t2g
Selain s-donor - akseptor bisa jadi tidak mematuhi aturan 18
elektron

29

Perkecualian untuk Zn(en)32+ (spesies dgn 22 elektron)

* orbital t2g dan eg terisi.

* en merupakan s-donor yg tdk sekuat ligan CO maka elektron
pada orbital eg tidak cukup antibonding, dan bisa ditempati dengan
stabil dengan penambahan 4 elektron

30

TiF62- (Spesies dengan 12 elektron)

Ligan F- merupakan ligan dengan -donor sebaik s-donor.
-donor pada F- mendestabilisasi orbital t2g sehingga agak antibonding
Spesie TiF62- mempunyai 12 elektron pada orbital s bonding dan tidak ada
elektron pada orbital antibonding t2g dan eg
Konfigurasi 18 elektron kompleks stabil dengan ligan -akseptor yang kuat .
Termasuk utk geometri trigonal bipyramida (Fe(CO)5) dan geometri
tetragonal (Ni(CO)4).
Untuk geometri square planar, konfigurasi yg stabil adalah 16 elektron.
Khususnya utk kompleks logam d8

31

Kompleks dengan aturan 16 e

Biasanya unsur blok d diseb. kanan khususnya group 9 dan 10
Tabel senyawaan organologam dgn aturan 16 dan 18

Biasanya < 18 e
Sc
Y
La

Ti
Zr
Hf

V
Nb
Ta

Biasanya 18 e
Cr
Mo
W

Mn
Tc
Re

Fe
Ru
Os

16 atau 18 e
Co
Rh
Ir

Ni
Pd
Pt

32

PERHITUNGAN ELEKTRON DLM KOMPLEKS

Cr(CO)6

Cr
6 CO
Total

6e
12 e
18 e

Fe(CO)4PPh3

Fe
4CO
PPh3
Total

8e
8e
2e
18 e

36

Ni(PF3)4

[Mn(CO)5]-

[Co(CO)4]-

Mn2(CO)10

Ni
4 PF3
Total

10 e
8e
18 e

Mn
5 CO
Muatan
Total

7e
10 e
1e
18 e

Co
4 CO
Muatan

9e
8e
1e

2 Mn
10 CO
Mn Mn
Total

14 e
20 e
2e
36 e

Co2(CO)8

2 Co
8 CO
Co Co
Total

18 e
16 e
2e
36 e

[PtCl4]2-

Pt
4 Cl
Muatan
Total

10 e
4e
2e
16 e

HMn(CO)5

Mn
5 CO
H
Total

7e
10 e
1e
18 e

37

38

39

Tentukan electron counts dengan kedua metode untuk

a. [Fe(CO)42b. [(5-C5H5)2Co]+
c. (3-C5H5)(5-C5H-5-)Fe(CO)
d. Co2(CO)8 (satu ikatan bridging Co-Co)
e. IrCl(CO)(PPh3)2
dengan membandingkan beda hasil kedua metode perhitungan
electron tentukan logam transisi deret pertama untuk kompleks 18
elektron (kecuali e. 16 elektron)berikut
a. [M(CO)3PPh3]b. HM(CO)5
c. (4-C8H8)M(CO)3
d. [(5-C5H5)2(Co)3]2
e. [M(CN)4]2-

40

Aturan 18 Elektron
Q : Ngapain repot-repot ngitung elektron?
A : Dasar untuk mempelajari struktur dan
reaktivitas reaksi organologam.
Tidak beda jauh dari struktur Lewis.
Maka,perhitungan seharusnya otomatis,
perhitungan seharusnya bukan dengan
menghapal ligan tapi memahami
karakteristik sharing elektron dalam
kompleks
41

Perkiraan Reaktivitas
- C2H4

dissociative
(C2H4)PdCl2

(C2H4)2PdCl2
CO

CO

?
(C2H4)2(CO)PdCl2
associative

(C2H4)(CO)PdCl2
- C2H4

Most likely associative:

16-e PdII

16-e PdII

18-e PdII
42

Perkiraan Reaktivitas
- CO
Cr(CO)6
MeCN

dissociative
Cr(CO)5

MeCN

Cr(CO)6(MeCN)
associative

Cr(CO)5(MeCN)
- CO

Almost certainly dissociative:

16-e Cr(0)

18-e Cr(0)

18-e Cr(0)
43

Electron counting
Q : Terus kalo saya ngitung elektron hasilnya 16
atau 14 artinya apa?
A : Struktur dengan elektron count dibawah ideal
disebut kekurangan elektron (electrondeficient )atau tidak jenuh (coordinatively
unsaturated).
Mempunyai valence orbitals(orbital kosong) .
Membuatnya bersifat elektrofilik, bisa diserang
nukleofilik.
Bisa sangat reaktif, menyerang hidrokarbon
atau mengikat gas mulia
44

Reactivity of electron-deficient compounds

Fe(CO)5

18-e Fe(0)
unreactive

h
- CO

Fe(CO)4 THF

16-e Fe(0)
very reactive

Fe(CO)4(THF)

18-e Fe(0)

45

Q : Trus kalo electron counting ketemunya lebih dari

18, terlalu banyak maksudnya apa?
A : Jumlah net kovalen bonds kecil
valenceorbital tidak cukup tersedia untuk elektron ini

An ionic model is required to explain part of the

bonding.
Ikatan bersifat lemah
Relatif jarang untuk logam transisi, biasanyaterjadi
karena reduksi (= penambahan elektron).
Elektron bisa berada pada L-M bonding orbitals
atau pada metal-centered lone pairs.
Metal-centered orbitals punya energi tinggi
atom metal dengan suatu lone pair adalah s-donor
(nucleophile).

46

Cara Mempercepat Electron Counting

Belajar mengenal muatan dan donor untuk ligan umum
Cationic 2e- donor: NO+ (nitrosil)
Neutral 2e- donors:
PR3 (phosphines), CO (carbonyl),
R2C=CR2
(alkenes), RCCR (alkynes, can also
donate
4 e-), NCR (nitriles)
Anionic 2e- donors: Cl- (chloride), Br- (bromide), I- (iodide),
CH3- (methyl), CR3- (alkyl), Ph- (phenyl), H(hydride)
bisa donor 4 e- tapi untuk perhitungan awal hitung sebagai2edonors (kecuali jadi bridging ligands): OR- (alkoxide), SR(thiolate), NR2- (inorganic amide), PR2(phosphide)
Anionic 4e- donors: C3H5- (allyl), O2- (oxide), S2- (sulfide), NR2(imido), CR22- (alkylidene)
and from the previous list: OR- (alkoxide),
SR- (thiolate), NR2- (inorganic amide), PR2 Anionic 6e- donors: Cp- (cyclopentadienyl), N3- (nitride)
47

Ligands, Charges, and Donor #s

48

Ligands, Charges, and Donor #s

49

Lewis Base Ligands -- Halides

Increasing polarizability

F , Cl , Br , I
Primary Halides

2e- terminal

Strongest nucleophile
for low oxidation state
metals centers

X
M

4e- m-bridging

M
6e- m3 -bridging

Common Misconception: The halides are anionic ligands, so they are NOT

electron-withdrawing ligands. In organic chemistry the halogens can be

considered neutral ligands and do drain electron density from whatever they are
attached to. But here they are anionic and are perfectly happy with that charge.
Their electronegativity makes the halides poor donor ligands. As one moves
from F- to I-, the donor ability increases as the electro-negativity drops.
50