Coordination Chemistry Concepts and Applications

Coordination Chemistry
Yessi Permana

Coord. Chem. in Nature
Coord. Chem. in Nature
Hemoglobin
Type of Ligands
N N
Monodentate
Bidentate
Tridentate
etc
(keyword: chelate)
P
triphenylphosphine
phenanthroline
N
N
O
-
O
O
-
O O
-
O
O
O
-
EDTA
Nomenclature
Anionic
Ligands
Names Neutral Ligands Names
Br
-
bromo NH
3
ammine
F
-
fluoro H
2
O aqua
O
2-
oxo NO Nitrosyl
OH
-
Hydroxo CO Carbonyl
CN
-
cyano O
2
dioxygen
C
2
O
4
2-
oxalato N
2
dinitrogen
CO
3
2-
carbonato C
5
H
5
N pyridine
CH
3
COO
-
acetato H
2
NCH
2
CH
2
NH
2
ethylenediamine
Nomenclature
Number Prefix Number Prefix Number Prefix
1 mono 5 penta
(pentakis)
9 Nona
(ennea)
2 di (bis) 6 hexa
(hexakis)
10 deca
3 tri (tris) 7 hepta 11 undeca
4 tetra
(tetrakis)
8 octa 12 dodeca
Numerical prefixes

Nomenclature
Name of Metal Name in an Anionic Complex
Iron Ferrate
Copper Cuprate
Lead Plumbate
Silver Argenate
Gold Aurate
Tin Stannate
Cobalt Cobaltate
Name of Metals in Anionic Complexes

Isomerism
Cis/Trans & Facial/Meridional

Optically Active (chiral)

. = (Left handed rotation); A = o (Right handed rotation). Rotations are all with respect to the plane of polarized light.
Test 1
A. Give the systematic names for the following coordination compounds:
1. [Cr(NH
3
)
3
(H
2
O)
3
]Cl
3

2. [Pt(NH
3
)
5
Cl]Br
3

3. [Pt(H
2
NCH
2
CH
2
NH
2
)
2
Cl
2
]Cl
2

4. [Co(H
2
NCH
2
CH
2
NH
2
)
3
]
2
(SO
4
)
3

5. K
4
[Fe(CN)
6
]
B. Give the molecular formulas of the following coordination compounds:

1. hexaammineiron(III) nitrate
2. ammonium tetrachlorocuprate(II)
3. sodium monochloropentacyanoferrate(III)
4. potassium hexafluorocobaltate(III)
Crystal Field Theory
Description of Theory:

1. Basic Assumption: Metal & Ligands are charged particles.
2. d Orbital will be splitted into two energy level (doubly gerade or eg and triply gerade
or t2g with respect to barrycenter with energy difference of Aoct ).
3. The difference of Aoct level will depend on the ligands (see spectrochemical series).
Crystal Field Theory
Spectrochemical Series
(Experimental data):

Impact:
High or Low Spin (HS / LS)

Energy is proportional to 1/

Crystal Field Stabilization Energy
(Octahedral)
Calc. of CFSE depend on the type of electron spin (High & Low-Spin).
In case of low-spin arrangement ; a Pairing Energy (P) must be considered.
Pairing energy is only contributed to the total CFSE when new electron pairs are required
in low-spin arrangement (no additional P is contributed in low-spin CFSE when a pair has
already exist in the high-spin arrangement.
Crystal Field for Tetrahedral
In the case of tetrahedral: 10D
q
< P
(most of the case, the complex is High-Spin & Paramagnetic (d
1
~ d
9
)
Why the ATd < AOct (i.e, ATd = 4/9 AOct) ?

-Number of Ligands
-Orientation of Ligands pointing to the metal center
Crystal Field for Square Planar
Square Planar complexes are widely observed with Ni
2+
, Pd
2+
, Pt
2+
, Cu
2+

Crystal Field for Octahedral vs SP
Square Planar complexes are widely observed with Ni
2+
, Pd
2+
, Pt
2+
, Cu
2+

Jahn Teller Distortions (Oct)
Observed for asymmetric electron(s) in octahedral orbital set of eg : d
4
HS, d
7
LS, d
9

Weakness of CFT
Assuming M L interactions as merely electrostatic interactions,

Providing no explanation of neutral complexes, e.g. Ni(CO)
4

Poorly explaining the spectrochemical series of NH
3
vs H
2
O ligands based on momen
dipoles (H2O = 1.84 debye. NH3 = 1.46 debye)

Poorly explaining why the t-acceptor ligands are strong field ligands
Test2
Molecular Orbital Theory
eg sets
t1g sets
a1g sets
px, py, pz
s
Complex with M L o Bonding (Octahedral case)
e.g. : [Co(NH
3
)
6
]
+

Complex with M L o Bonding (Octahedral case)
e.g. : [Co(NH
3
)
6
]
+

Complex with M L o , t Bonding
Complex with M L o , t* Bonding
Complex with M L o , t* Bonding (t2g set of LGO)
Complex with M L o Bonding (Octahedral case) e.g. : [Co(NH
3
)
6
]
+

Complex with M L t Bonding (Octahedral case)

Complex with M L t* Bonding (Octahedral case)

Ttg Ni(I), d
9
Test 3
Describe relative ligand field strength between t donation and t-acceptor
ligands.

e
g
*
t
2g

| | |
A
o
o bonds only
t
2g
*
t
2g

| | |
|+ |+ |+
A
o
|+ |+ |+
Filled ligand
group orbital
ML t bonding
(t donor ligand)
e
g
*
t
2g

t
2g
*
| | |
A
o
ML t bonding
(t acceptor ligand)
empty ligand
group orbital
e
g
*
Electronic Spectra
Aqua ions of high spin complexes
Fakta Serapan:
(A = c x c x l)
Transisi elektron yg mungkin pd kompleks oktahedral:
1. t2g ke eg (d-d)
2. orbital metal ke ligand (MLCT)
3. orbital ligand ke metal (LMCT)

Note: CT gives more intense absorption (higher c) than d-d
(A = c x c x l)

Electronic Spectra
Selection Rule
Aturan seleksi u/ transisi antar energi elektronik:

1. S = 0 The Spin Rule (Konsistensi Multiplisitas)
(note: Muliplicity = (2S + 1), described in singlet, doublet, triplet, etc

2. l = +/- 1 The Orbital Rule (Laporte)
Selection Rule
Aturan seleksi u/ transisi antar energi elektronik:

1. S = 0 The Spin Rule (Konsistensi Multiplisitas)
(note: Muliplicity = (2S + 1), described in singlet, doublet, triplet, etc

2. l = +/- 1 The Orbital Rule (Laporte)
Selection Rule
Aturan seleksi mengisyaratkan tidak adanya transisi antar orbital logam atau transisi d-d :
Bagaimana kompleks logam transisi berwarna-warni?

Usulan mekanisme :
1. d-d Laporte forbidden terjadi pada T = 0 K.
Pd kondisi alami terjadi vibrasi yang mengijinkan masuknya karakter p (transisi menjadi
d p; Vibronic coupling mechanism)
2. Mekanisme spin-orbit (Percampuran multiplisitas)
Ground term (Lowest Energy) : Highest multiplicity, highest M
L
in the same M
s
Microstates Octahedral d
2
Microstates Octahedral d
2
Ground term (Lowest Energy) : Highest multiplicity, highest M
L
in the same M
s
Thus: 3F < 3 P < 1G < 1D < 1S (applied in Orgel Diagram)
Spectroscopic observation for d2 of Ti(II) : 3F < 1D < 3P < 1G < 1S

Shriver&Atkins, Inorg.Chem., p.439 - 443
Clebsch-Gordan series:
L = l1+l2, l1+l2-1,
(d2 : L = 4, 3, 2, 1, 0)

S = s1+s2, s1+s2-1,
(d2 : S = 1, 0)

Orgel Diagram
Term symbol :
(2S+1)
L
J
(2S+1): Multiplisitas; L: orbital (S, P, D, F,);
J : Total angular momentum (L+S), (L+S-1), (L-S)

Transition of spin-allowed only !
Orgel Diagram
Tiga transisi elektronik yang mungkin
Transisi selalu dari keadaan dasar (ground term)
Orgel Diagram
Orgel Diagram
Weakness of Orgel Diagram
Racah Parameter
Racah parameters were generated as a means to describe the
effects of electron-electron repulsion within the metal
complexes.

All terms include racah parameter A
Triplet terms exclude racah parameter C

If: C > 5B
Order of orbital energy similar to hunds rule :
3F < 3P < 1D < 1G < 1S
If: C < 5B , then: 1D < 3P (similar to observed fact of d2 Ti(II)
Diagram Korelasi
3
T
1g
3
T
2g
3
A
1g
1
T
2g
1
E
g
3
T
1g
1
A
1g
1
T
2g
1
T
1g
1
E
g
3
P
1
D
3
F
1
G
1
S
1
E
g
3
A
2g
1
E
g
3
A
1g
3
T
1g
1
T
2g
1
E
g
1
A
1g
3
T
2g
3
T
1g
1
T
2g
1
T
1g
t
2g
2
t
2g
e
g
e
g
2
Free ion
weak interaction
strong
interaction
strong
interaction
1 state

9 states

3 states

5 states

7 states

G L Miessler, Inorg. Chem., p.391.
Diagram Tanabe-Sugano (Racah Parameter B only)
Tingkat dasar diplot sepanjang sumbu datar. Digunakan untuk interpretasi spektrum
elektronik senyawa kompleks.
0 10 20 30 40
10
30
50
E/B
A
o
/B
3
T
2g
3
T
1g
3
T
1g
3
A
2g
3
F
3
P
Diagram Tanabe-Sugano untuk d
2
.
Spektrum absorpsi komplek d
2
[V(H
2
O)
6
]
3+
.
Terdapat dua puncak serapan dari tiga puncak
yang diperkirakan, satu puncak berada jauh di
kanan.
Diagram T-S untuk d
2
d
8
yang lain dapat dilihat
pada G L Miessler, Inorg. Chem., p.368.
v
1
v
2
v
3
v
1
v
2
Tanabe-Sugano (racah parameter B only)
Y. Tanabe, S. Sugano, J. Phys.Soc. Jpn, 1954, 9, 766
Tanabe-Sugano (racah parameter B only)
Y. Tanabe, S. Sugano, J. Phys.Soc. Jpn, 1954, 9, 766
Jahn Teller Distortions & Spectra
Bagaimana dengan kompleks d
1
dan d
9
?
Keduanya hanya memiliki satu peluang eksitasi t
2g
ke e
g
, diharapkan hanya ada satu puncak
serapan. Spektrum kompleks d
1
dan d
9
menunjukan adanya dua puncak yang berdekatan.
|
|
|
|+ |+ |+
|+
| |+ |+
|+ |+
d
1
d
9
Efek Jahn-Teller terjadi pada orbital degenerate yang terisi secara tak-simetris, seperti d
1

dan d
9
di atas.
|
|+ |+ |+
|+
d
z
2
d
x
2
-y
2
Efek Jahn-Teller pada d
9
.
Ada dua peluang eksitasi yang dapat
terjadi, menghasilkan dua puncak
serapan.
Diagram Tanabe-Sugano
Bagaimana dengan kompleks d
1
dan d
9
?
Keduanya hanya memiliki satu peluang eksitasi t
2g
ke e
g
, diharapkan hanya ada satu puncak
serapan. Spektrum kompleks d
1
dan d
9
menunjukan adanya dua puncak yang berdekatan.
|
|
|
|+ |+ |+
|+
| |+ |+
|+ |+
d
1
d
9
Efek Jahn-Teller terjadi pada orbital degenerate yang terisi secara tak-simetris, seperti d
1

dan d
9
di atas.
|
|+ |+ |+
|+
d
z
2
d
x
2
-y
2
Efek Jahn-Teller pada d
9
.
Ada dua peluang eksitasi yang dapat
terjadi, menghasilkan dua puncak
serapan.
Magnetic Moment
Nephelauxetic Effect
d-Block complexes (descriptive)
Relative abundance in Earths crust.
Note: 1 oz of gold = 1300 usd
Fakta: Ti adalah LT yang paling banyak aplikasinya; bahan pesawat militer dan kapal selam
nuklir. Zr digunakan untuk kontainer bahan bakar nuklir karena tidak menyerap netron.
Sifat: keras, putih berkilau, paling ringan di antara LT, strength-to-weight ratio tertinggi, tahan
korosi, logam paling melimpah no.9.

Recovery:
TiO
2
+ 2C + 2Cl
2
TiCl
4
+ 2CO
TiCl
4
+ 2Mg Ti + 2MgCl
2
Oksida, TiO
2
(rutile)
Senyawa Ti yang paling penting, inert dan nontoxic.
Digunakan untuk cet (warna putih), bahan cosmetics and pasta gigi.

Group Ti
Ti & Cr complexes in Apps
Ti in Ziegler-Natta Catalyst Cr in Phillips Catalyst
Cl
Mg
Cl
Mg
Cl
Mg
Cl
Mg
Cl
Cl
Cl Cl Cl Cl
Cl
Ti
Me
O
R
Cl
Si
OMe
Group Ti, V, Cr
Used extensively in PE productions
Pyrolide-Immine Complex (X = Cl) Phenoxy-Immine Complex (X = Cl)
Sc, Zr, Co (in searching of proper metal for
PGA Synthesis)
PGA Synthesis)
PGA Synthesis)
Zr
O
O
O
O
O
O
Ph
Ph
Ph
Ph
Ph
Cl
-
H
H
H
a
b
c
d
b
d
ZrCl
4
Ph
Ph
O
O
1c 2c
PGA Synthesis)
PGA Synthesis)
Mn, Co in carbonylation
Used in Carbonylation apps
Co in carbonylation
[Al(salph)L
2
][Co(CO)
4
]
(0.5 mol%)
toluene, 80 C, 24 h
G.W. Coates et al. J. Am. Chem. Soc. 2002 124, 6842
O
O
O
+ CO
14 atm
> 99% conv.
R. A. Grey, D. Armstead, US Patent, 5401857, 1995
O
O
CO +
HO
[Rh
6
(CO)
16
/ Pyridine
Toluene, 12 h, 60 C
3 - 20 atm
O
32% conv. 43 : 57 (no C4 products)
Co, Rh in carbonylation
Zn (poor oxophilicity)
Used in Carbonylation apps
Behavior in Water, case of V
Behavior in Water, case of V
Polyoxometalates
[V
4
O
12
]
4
Tetrahedral structure of VO
4
unit

[V
18
O
42
I]
5
Ligand Substitution
(Reaction Mechanism)

M.C. White ppt, 2002, Crabtree, 2005, Housecroft, 2008, I.N. Marsih ppt
Complex with M L o Bonding (Octahedral case) e.g. : [Co(NH
3
)
6
]
+

Aturan 18-elektron
18-elektron max
Complex with M L t Bonding (Octahedral case)

Aturan 18-elektron
18-elektron max
Complex with M L t* Bonding (Octahedral case)

Aturan 18-elektron
18-elektron max
Aturan 18-elektron
Analog dengan aturan oktet pada struktur titik Lewis, pada senyawa LT berlaku
aturan 18-elektron. Komplek yang stabil akan terbentuk jika
elektron valensi dari atom pusat + elektron dari ligan + muatan = 18
Contoh:
Ni(CO)
4
Ni(0) 10 e

4 x CO 4 x 2 e

Total 18 e
Mn(CO)
5
Br

Mn(I) 6 e
5 x CO 5 x 2 e

Br
2 e
Total 18 e
Fe(Cp)
2

Fe(II) 6 e
2 x Cp
-
2 x 6e
total 18 e
Fe
Aturan 18-elektron
k
: ligan yang berikatan dengan k atom logam (bridging ligand)
Contoh:

(q
3
-C
7
H
7
)Fe(CO)
3
(OC)
3
Fe
Fe
2
(
2
-CO)
2
(CO)
6
(OC)
3
Fe Fe(CO)
3
C
O
C
O
Symbols

q
n
: menyatakan ada n atom karbon dari ligan yang berikatan dengan atom pusat.
Contoh:
Free CO : vCO = 2143 cm
-1
Case of (CO)
3
AcCo-PR
3
(FT-IR)

Co
O
OC
OC
CO
P(OPh)
3
Co
O
OC
OC
CO
P(p-tol)
3
Co
O
OC
OC
CO
P(NMe
2
)
3
Co
O
OC
OC
PPh
2
Ph
2
P
Electron density on Co:
AcCo(CO)
3
P(OPh)
3
< AcCo(CO)
3
P(p-tol)
3
< AcCo(CO)
3
P(NMe
2
)
3
<

AcCo(CO)
2
dppp

vCO

vCO
(acyl)
1958
1971
1944
1911
1663
1676
1655
1628
(Strong vCO)
(Weak vCO)
v (cm
1
) v (cm
1
)
Longer Co C1 bond length = Weaker back-donation from Cobalt to CO
Electron density on Co :
AcCo(CO)
3
P(OPh)
3
< AcCo(CO)
3
P(p-tol)
3
< AcCo(CO)
2
dppp
C1
Co
P
P
O
O
O
C1
Co
P
O
O
O
O
C1
Co
P
O
O
O
O
O
O
O
P(OPh)
3

P(p-tol)
3

dppp

2.039(3) 2.0077(18) 1.985(3)
Case of (CO)
3
AcCo-PR
3
(Single-Crystal XRD)

Avoiding |-H Elimination on polyolefin process
ZrCl
2
cat 2
O
TiCl
2
cat-3
[437.22]
[418.7]
O
N
TiCl2
2
[623.35]
cat-1
(Toluene 250 mL, 25 C)
n
o-H Elimination
|-alkyl Elimination

Isikan step reaksi berikut:
3
ox.add.
r.e.
r.e.
(ease exchange of I
and PPh
3
for CF
3
to
give 6 in the
presence of A or B)
6
ox.add.
ox.add.
5
E
F
G
Isikan step reaksi berikut:
TS-1B
E
a
= 25.15 kJ/mol
v = 518.87 cm
-1
3A
Y. Permana, N. P. Indriyani, Arifin, M.A. Martoprawiro, E. Gokturk, S. Miller, to be submitted
E
a
= 28.37 kJ/mol
v = 594.80 cm
-1
TS-1A
O
O
n
Branched
O
O
n
Linear (major)
3A
1,2 or 2,1-insertion?
Putih: H
Biru: Co
Abu2: C
Merah: O

CO Insertion (Alkyl Migration)
CO insertion
Alkyl migration
(supported by NMR exp and calculation)
(Disapproval of outer-sphere insertion)
Condition for carbonylation to occur:
Carbonylation requires coordinated CO
Migratory de-insertion
CO Insertion (Alkyl Migration)
Combinging Olefin & CO insertions + Ox.Add/Red. Elim
-CO
CO
Carbene Metals
Carbene Metals
Fischer Schrock
Grubbs I
Grubbs II
Carbene Complexes
Nobel Prize 2005
O
O
O
O
O
O OH
OH
OH
HO OH
OH
O
H
HO
HO
O OH
O
6
5
300 C
HO
O
HO
O
+
+
(Reduction)
(Pyrolysis)
H
2
O
2H
2
O
H -Transfer
O
OH
300 C
SBA-SO
3
H
93%
Fe
2
O
3
25%
F. Schuth, et al. Chem. Commun. 2010 46 1238-1240
Renewable Resources for Biorefinery Oil
J.P Lourenco, et al.
Catal. Commun. 2012 19 105-109
Castor Plant
(Ricinus Communis)
C.V. Stevens, et al. Eur. J. Lipid Sci. Technol. 2008 110 846--52
M.A.R. Meier, et al. Eur. J. Lipid Sci. Technol. 2010, 112, 10-30
Grubbs Processes (..in Gresik !)
Worlds largest biorefinery by metathesis technology in Gresik started on July 2013
US-based
Inc
Singapore
based Inc
Grubbs Company
Cross-Coupling ; Basic Principle
R X
R' M
R R'
+
Cat.
- MX
Ligands :

1) OPTIMUM: PCyp
3
(Cyp = Cyclopentyl).
2) MODERATE: PCy
3
& PiPr
3
.
3) POOR Ligand: NHC-1
N N
Fig. 1.
1
Cl
Cross-Coupling for sp
3
; Tougher than sp
2

Ex. Negishi Reaction:
R
+
R'-ZnBr R
X
R'
2% [Pd
2
(dba)
3
]
8% ligand
1.2 eq NMI
2:1 THF/NMP
80
o
C, 14 h
X = I, Br, Cl, OTs
H
H
1.3 eq.
G.C. Fu J. Am. Chem. Soc. 2003 125 12527
X = I; R =n-Dec (87%)
X = Br; R =n-Dec (90%)
X =Cl; R =n-Dec (97%)
X = OTs; R =n-Dodec (86%)
For PCyp
3
ligand
and R' = n-Bu:
Catalysis

Polyolefin Processes
Plastic Consumption (Asean)
Type of Plastic Consumption (Indonesia)
Schematic Industrial Process
Polypropylene & Isomerizations
Coordination Catalysts for Olefin Polymerizations
Factors Affecting the Performance
Multi-site Catalysts
Catalyst System:
THC catalyst TiCl
4
/ Internal Donor / MgCl
2

pre-polymerization THC External DonorC4 AlEt
3
(THC/C4)
polymerization THC/C4 External DonorDC) + AlEt
3

MeO
OMe
Si
OMe
OMe
DC
C4
Cl
Mg
Cl
Mg
Cl
Mg
Cl
Mg
Cl
Cl
Cl
Cl Cl Cl
Cl
Ti
Me
O
R
Cl
Si
OMe
Tanaka Y., Sci. Tech. Catal., 2006, 527-528
Sacchi M.C., Macromolecules, 1996, 3341-3345
Moderate Isotacticity
Excellent H
2
-Response
Poor H
2
-Response
Excellent Isotacticity
Donor Properties:
Isospecific-Site
for Propylene
DC-Donor
(Isotactic control on Ziegler-Natta catalyst by donors)
Ziegler Natta Cat in PP Production
Single-site Catalysts: Metallocenes
ansa-metallocenes (ansa = handle)
Evolutions of Metallocenes in PP Productions
Evolutions of Metallocenes vs Performance
Roles of Cocatalyst
Vacant site formation
Co-catalysts: Methyl Aluminoxane (MAO)
Type: DMAO (dried), MMAO (modified)
Avoiding |-H Elimination on polyolefin process
ZrCl
2
cat 2
O
TiCl
2
cat-3
[437.22]
[418.7]
O
N
TiCl2
2
[623.35]
cat-1
(Toluene 250 mL, 25 C)
n
Metathesis Catalysis
Metathesis Catalysis - Chauvins Processes
Metathesis Catalysts: Carbene Metals
In 1960s
in 1970s (3 proposed mechanisms)
No cyclobutane as
products; Added
cyclobutane was not
participated in the
reactions.
Grubbs proposal;
Unclear
rearrangement of
intermediate.
Unreasonable
teramethylene
metal.
Pairwise Mechanisms
two alkenes simultaneously bound to the metal
Chauvins Experiments
Pairwise Mechanisms (proved misconceived)
Double cross product
No double cross product should appear in the beginning
Chauvins Proposal: Non-Pairwise Mechanisms
alkenes were converted one at a time
Non-Pairwise Mechanisms
Hydroformylation
Hydroformylation
Hydroformylation
Hydroformylation
M. Torrent, M. Sola, G. Frenking, Chem. Rev. 2000 100 439-493.
Monsanto Acetic Acid Process
Thermodynamically possible
Yet, it requires 700 atm of CO (300 C) to proceed by Co / I.
Milder route by Rh / I
(150 C, 30 atm CO).
Production:
6.5 million ton / year
Monsanto Acetic Acid Process (weakness)
Note: 1 oz of gold = 1300 usd
Rhodium is an expensive starting material.
1 mole of RhCl
3
.
3H
2
O costs ~ $30,000!
Monsanto Acetic Acid Process (Iridium cat)
A. Successful couplings of simple halides ( sp3-hybridized carbons) is rare. Why ?

B. How to increase the rate of oxidative addition of alkyl or aryl halides?
Quiz : Cross-Coupling
Wacker Catalytic Process

Coordination Chemistry Concepts and Applications

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