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KIMIA ORGANOLOGAM

LIGAN-LIGAN DALAM
KIMIA ORGANOLOGAM
IV. Ligan-ligan Dalam Kimia Organologam
Hampir seratus ligan lebih diketahui membentuk ikatan antara
logam dan karbon.

Beberapa ligan yang banyak dikenal membentuk senyawa


organologam antara lain :

1. Ligan karbonil
2. Senyawa organik yang mempunyai sistem  linier dan  - siklis
3. Kompleks karbena (membentuk ikatan rangkap tiga antara
atom logam dan karbon).
4. Kompleks karbuna (membentuk ikatan rangkap tiga antara
atom logam dan karbon).

Ad.1. Kompleks Karbonil


Karbon monoksida merupakan ligan yang paling umum dalam
senyawaan organologam.
Ligan karbonil umumnya mengikat satu atom logam dan juga
dapat bertindak/berfungsi sebagai ligan jembatan dengan
mengikat dua atau lebih atom logam.
Dalam sub bab ini akan dibahas tentang :
- Ikatan antara logam dengan ligan karbonil
- Sintesis dan beberapa reaksi dari kompleks karbonil
- Beberapa contoh pembuatan kompleks karbonil

IKATAN LIGAN KARBONIL


Untuk membentuk ikatan ligan karbonil memanfaatkan bentuk
orbital atom 2p. Bentuk molekul CO dapat dilihat pada gambar
dibawah :
Ada dua hal yang perlu diperhatikan pada gambar orbital molekul
dari ligan karbonil diatas :
1. Orbital dengan tingkat energi tertinggi yang terisi elektron
(HOMO) mempunyai “lobe” paling besar pada atom karbon
melalui orbital ini yang terisi sepasang elektron akan
berfungsi donor  pada ligan CO kepada orbital kosong dari
logam (seperti p, d, atau orbital hibrid).
2. Orbital dengan tingkat energi terendah yang tidak terisi
elektron (LUMO), ligan CO mempunyai dua orbital  anti
bonding (*) yang juga mempunyai “lobe” lebih besar pada
atom karbon daripada atom oksigen. Adanya orbital kosong
ini menyebabkan ligan karbonil bertindak sebagai  aseptor.
Dimana ikatan dari donor  dan -aseptor dapat digambarkan
sebagai berikut :
Jika benar terjadi ikatan antara ligan CO dengan atom logam, hal
itu harus didukung oleh hasil eksperimen.
Ada dua bukti eksperimen yang dapat digunakan :
1) spektroskopi IR dan, 2) X-ray kristalografi.
1) Adanya ikatan logam-karbon (M-C) dapat diamati dari
perubahan vibrasi ulur dari C-O dimana :
C-O bebas 2143 cm-1
C-O dalam [Cr(CO)6] 2000 cm-1

 =k/ dimana :  = (m1.m2)/(m1+m2)


Adanya ikatan  dan  aseptor akan memperlemah ikatan antara
C-O, sehingga harga  juga menjadi menurun.

Muatan dari kompleks karbonil juga mempengaruhi harga


bilangan gelombang dari gugus CO, contoh :
Kompleks  (CO), cm-1
[V(CO)6]- 1858
Cr(CO)6 2000
[Mn(CO)6]+ 2095
2) Bukti dari data X-ray kristalografi
Untuk C-O bebas mempunyai panjang ikatan 112,8 pm.
Dengan adanya pembentukan ikatan antara logam dengan
ligan karbonil akan memperlemah ikatan C-O ini terlihat
dengan semakin panjangnya jarak ikat C-O menjadi : 115 pm

MODEL JEMBATAN DARI LIGAN KARBONIL


Meskipun secara umum ligan CO membentuk ikatan tunggal
dengan atom logam, tetapi dari beberapa kasus yang ada
diketahui ligan CO dapat membentuk jembatan antara dua atau
lebih atom logam. Beberapa contoh model jembatan seperti
terlihat pada contoh tabel dibawah :

Tabel …. Beberapa model jembatan dari ligan CO


O O
O C O C M C C
M M
M M M
free CO terminal mode 2 bridging 3 bridging

CO IR (cm -1 ) 2143 2120 - 1850 1850 - 1720 1730 - 1500


(for neutral metal complexes)
M-C bond: increases increases increases
C-O bond: increases decreases decreases
CO freq: increases decreases decreases

Carbonyl IR Stretching Frequencies


• The position of the carbonyl bands in the IR depends mainly on the bonding
mode of the CO (terminal, bridging) and the amount of electron density on the
metal being -backbonded to the CO.
• The number (and intensity) of the carbonyl bands one observes depends on the
number of CO ligands present and the symmetry of the metal complex. There
are also secondary effects such as Fermi resonance and overtone interactions
that can complicate carbonyl IR spectra.
Effect of Electron Density on Metal:
Effect of Electron Density on Metal:

As the electron density on a metal center increases,


more -backbonding to the CO ligand(s) takes place. This
futher weakens the C-O bond by pumping more electron
density into the formally empty carbonyl * orbital. This
increases the M-CO bond strength making it more double-
bond-like, i.e., the resonance structure M=C=O assumes
more importance.
dx Complex CO cm-1
This can clearly be seen on free CO 2143
the table to the right that d10 [Ag(CO)]+ 2204
illustrates the effect of charge Ni(CO)4 2060
and electronegativity on the [Co(CO)4]- 1890

amount of metal to CO -back- [Fe(CO)4]2- 1790


[Mn(CO)6]+ 2090
bonding and the CO IR d6 Cr(CO)6 2000
stretching frequency. [V(CO)6]- 1860
Shown below is another example of the dramatic effect on the CO IR stretching
frequencies on reducing Fe2(-PPh2)2(CO)6 by 2 electrons to form the dianionic
complex [Fe2(-PPh2)2(CO)6]2-. The average CO frequency shifts almost 150 cm-1
to lower energy on reduction.

Ph2 Ph 2
P P
Ph 2 2-
OC CO O O
Fe Fe C P C
OC CO
C C OC
Fe Fe CO
O O C P C
O Ph 2 O
2100 2000 1900 1800
Wavenumbers (cm -1)
The carbonyl region in the IR spectrum can be very distinctive and useful for
help in assigning structures and for indicating the relative amount of electron
density present on the metal (dppm = Ph2PCH2PPh2, Ph groups not shown on
structural drawings below):

O
OC C CO
Ni2 (  -CO)(CO) 2(dppm) 2 Ni Ni
P P

-CO +CO P P

P P
Ni 2(CO) 4(dppm) 2 OC CO
Ni Ni
OC CO
P P

-CO +CO

P P
2 Ni(CO) 3(  -dppm)
1 OC
Ni
OC
C
O

2000 1900 1800 1700


Wavenumbers (cm-1 )
Ligand Donation Effects:
Ligand Donation Effects:

The ability of the ligands on a metal to Complex CO cm-1


donate electron density to the metal
Mo(CO)3(PF3)3 2090, 2055
center certainly has considerable effect on
the absolute amount of electron density on Mo(CO)3(PCl3)3 2040, 1991
that metal. This, in turn, naturally effects Mo(CO)3[P(OMe)3]3 1977, 1888
the CO IR stretching frequencies in metal
carbonyl complexes. Ligands that are Mo(CO)3(PPh3)3 1934, 1835
trans to a carbonyl can have a particularly Mo(CO)3(NCCH3)3 1915, 1783
large effect on the ability of the CO ligand Mo(CO)3(triamine)3 1898, 1758
to effectively -backbond to the metal. For
example 2 trans -backbonding ligands Mo(CO)3(pyridine)3 1888, 1746
will partially compete for the same d-
orbital electron density, weakening each
others net M-L -backbonding.
When the trans ligand is a -donating ligand, this can increase the M-CO
bond strength (more M=C=O character) by allowing unimpeded metal to CO
-backbonding. Pyridine and amines are not that strong -donors, but they
are even worse -backbonding ligands. So the CO has virtually no
competition for -backdonation.
Based on CO IR stretching frequencies, the following ligands can be ranked
from best -acceptor to worst:
NO+ > CO > PF3 > RNºC > PCl3 > P(OR)3 > PR3 > RCºN > NH3
Semi-Bridging Carbonyls:

Unsymmetrical bridging form. * system accepts O


electron density from second metal center. Usually ~ 150

accompanied by distortions away from a linear M-CO C


(180°) or a symmetrically bridging CO (120°). Typical
M-CO angle around 150° (but with consider
variations). M M
Example: Substituting 2 carbonyls filled Fe d orbital
in Fe2(-CO)2(CO)6 with a bipy ligand O
leads to a considerable change in O O
the structure, particularly in the C C C
bridging CO region. The better - Cotton & Troup
JACS, 1974, 96, 1233
donating bipy ligand increases the e-
density on that Fe atom. This C
Fe Fe
O N
generates an asymmetrically
charged complex. The higher partial C C
negative charge on the bipy-
N
substituted Fe center can be O O
reduced by dumping some of it
specifically into the * orbital of one
of the bridging carbonyls, turning it CO * empty antibonding
into a semi-bridging CO. acceptor orbital
s/p Bridging CO :

This is where the CO not only acts as a traditional s-donor/p-acceptor


to one or more metal centers, but also as a p-donor to additional
metals. This will occur for more electron deficent metal complexes
where the metal centers have less need to p-backbond to the carbonyl,
but have the empty orbitals to accept electron density from the
carbonyl p-system. The CO ligand here can act as a 4 or 6 electron
donor!

O O O
C C C
M M M M M M
M M
Contoh Senyawa Netral Komplek biner karbonil logam

4 5 6 7 8 9 10 11

Fe(CO)5 Co2(CO)8
Ti V(CO)6 Cr(CO)6 Mn2(CO)10 Fe2(CO)9 Co4(CO)12 Ni(CO)4 bonilC
Fe3(CO)12 u

Nb Mo(CO)6 Tc2(CO)10 Ru(CO)5 Rh4(CO)12


Zr Ru3(CO)12 Rh6(CO)16 Pd Ag

Hf Ta W(CO)6 Re2(CO)10 Os(CO)5 Ir4(CO)12 Pt Au


Os3(CO)12
Color mp °C Sym IR CO cm-1 Misc
V(CO)6 blue-black 70(d) Oh 1976 paramagnetic, S = 1/2
Cr(CO)6 white subl Oh 2000 Cr-CO = 1.91 Å, air-stable
Mo(CO)6 white subl Oh 2004 Mo-CO = 2.06 Å, air-stable
W(CO)6 white subl Oh 1998 W-CO = 2.06 Å, air-stable in solid
state.
Mn2(CO)10 yellow 154 D4d 2044, 2013, 1983 Mn-Mn = 2.89 Å, bond is easily
broken.
Tc2(CO)10 white 160 D4d 2065, 2017, 1984 Tc-Tc = 3.03 Å
Re2(CO)10 white 177 D4d 2070, 2014, 1976 Re-Re = 3.04 Å
Fe(CO)5 yellow -20 D3h 2034, 2013 bp = 103°C, toxic, Fe-CO (ax) = 1.81
Å, Fe-CO (eq) = 1.83 Å, h produces
Fe2(CO)9
Fe2(CO)9 gold plates d D3h 2082, 2019, 1829 Fe-Fe = 2.46 Å, insoluble in most
solvents except for THF where is
dissociates to produce Fe(CO)4 +
Fe(CO)5
Fe3(CO)12 green d low complex
Ru(CO)5 colorless -16 D3h 2035, 1999 unstable, forms Ru3(CO)12
Ru3(CO)12 orange 150(d) D3h
Os(CO)5 colorless 2 D3h 2034, 1991 v. unstable, forms Os3(CO)12
Os3(CO)12 yellow D3h
Co2(CO)8 orange-red 51(d) D3d 2107, 2069, 2042, 2031, solid state structure has 2 -CO’s
2023, 1991 (1886, 1857 cm-1). Solution
structure is unbridged. Co-Co = 2.54
Å in solid-state.
Rh4(CO)12 red C3v 3 -CO’s around one triangular Rh3
face.
Ni(CO)4 colorless -25 Td 2057 bp 34°C, highly toxic, CO’s quite
labile, Ni-CO = 1.84Å
Problem: Consider the example below, do you think that the bridging
CO should act more as a -donor or -acceptor?

CO acting as -donor or -acceptor?


1.30Å
2.22Å 2.25Å O
O
O C C 1.97Å
C
Nb Nb Cp
Cp
C Nb C
O
O
Cp C C
O
O
Herrman & coworkers
JACS, 1981, 103, 1692
Problem: Which of the following
metal carbonyl IR spectra represents
the compound with the least amount
of electron density on the metal
center? Briefly discuss the
reasoning for your choice. Which
compound will lose CO the easiest?

a) CO
b)
CO
F CO Br CO
Ir Ir
F CO Br CO
F Br Problem: Which of the following metal
carbonyl compounds will have the
highest CO stretching frequency in the
c) CO IR? Why? Will this be the most electron-
rich or deficient compound?
Me2N CO
Ir
Me2N CO
NMe2
Ligan Hidrida
bridging mode
M
H anionic 2e donor {M H
M
H

1e to each M

Hydride nomenclature comes from the NMR behavior:

M-H ~ -5 to -25 ppm for d1 d9 metals!!


upfield shift indicates “hydridic” chemical
nature
HCo(CO)4 1H NMR = -10.7 ppm

BUT: HCo(CO)4 H+ + Co(CO)4-

strong acid in H2O, MeOH


similar to HCl !!
d0 Cp*2ZrH2 d = + 7.5 ppm
d10 [HCu{P(p-tolyl)3}]6 d = + 3.5 ppm

The presence of partially filled d orbitals on the transition metal has a


considerable shielding effect (moves the chemical shift of the NMR
resonance to more negative ppm) on the hydride 1H NMR chemical shift
position.
IR Spectra: M-H 2200 - 1600 cm-1 } can be very weak or absent
M2(-H) 1600 - 800 cm-1 } broader (weak or absent)

Late Transition Metals: tend to be more “protic”


Early Transition Metals: tend to be more “hydridic”
(plenty of exceptions; charge on complex important)
Early Transiton Metals Late Transition Metals
low electronegativities higher electronegativities
higher oxidation states lower oxidation states
“harder” metal centers “softer” metal centers
OXOPHILLIC!!
pKa Values for Transition Metal Hydrides in Various Solvents

Solvent
Metal Hydride Complex H2O MeOH CH3CN
HV(CO)6 strong acid
HV(CO)5(PPh3) 6.8
CpCrH(CO)3 5.4 13.3
CpMoH(CO)3 6.2 13.9
Cp*MoH(CO)3 17.1
CpWH(CO)3 8.0 16.1
CpWH(CO)2(PMe3) 26.6
HMn(CO)5 15.1
HRe(CO)5 ~21
H2Fe(CO)4 4.0 11.4
H2Ru(CO)4 18.7
H2Os(CO)4 15.2 20.8
CpFeH(CO)2 19.4
Cp*FeH(CO)2 26.3
CpRuH(CO)2 20.2
HCo(CO)4 strong acid strong acid 8.4
HCo(CO)3{P(OPh)3} 5.0 11.4
HCo(CO)3(PPh3) 7.0 15.4
HNi[P(OMe)3]4+ 1.5 12.3
HPd[P(OMe)3]4+ 1.0 8.0
HPt[P(OMe)3]4+ 10.2 18.5
H4Ru4(CO)12 11.7
H4Os4(CO)12 12.3
H2Ru4(CO)13 11.1
Problem: Which of the following pairs of metal
hydrides is the most acidic (lowest pKa )?

a) HRh(CO)(PEt3)2 -or- HCo(CO)(PPh3)2

b) HMn(CO)5 -or- HRe(CO)5

c) Cp2V(H)(NCMe) -or- [Ru(C6H6)(CO)2(H)]+

d) [HNi(CO)2(dmpe)]+ -or- [HPt(CO)2{P(OMe)3}2]+

e) CpFe(H)(CO)2 -or- CpOs(H)(CO)2