Chapter 3
Carbonyls, Phosphine Complexes
and Substitution Reactions
Outline
1. Metal complexes of CO
2. Metal complexes of CO-like ligands
:C O: :C
N-R
:C
S:
:N O:
:N N:
3. Phosphines as ligands
4. Substitution reactions
a). Dissociative substitution
b). Associative substitution
References and suggested readings:
1. The Organometallic Chemistry of the Transition Metals, Robert H.
Crabtree, 4th Edition, 2001, Chapter 4.
2. Organometallic Chemistry, G. O. Spessard, G. L. G. L. Miessler, PrenticeHall: New Jersey, 1997, Chapter 4.
3. Organotransition Metal Chemistry, Akio Yamamoto, 1986. Chapters 4.5,
6.1.
1. Metal complexes of CO
Why CO chemistry?
Current industrial raw material for carbon-based
chemicals:
Petroleum oil
Another possible carbon source:
coal
coal ------------> organic compound ?
C (coal) + H2O ---------> H2 + CO
(water gas)
catalyst
H2 + CO
CH3OH
useful products
hydrocarbons
[Link] structure of free CO
(1) In terms of valence bond theory
pz
sp
:
.
. . ..
C
px
sp
dipole moment:
px
= 0,
why?
sp
:C
..O:
or
:C
O:
(2) In terms of MO theory
Consider s-s, p-p mixing only :
4
2
3
LUMO
O 3
HOMO
1
C
1
2
O
1
O
2
HOMO: 3 orbital (a little
antibonding character,
localized on C)
LUMO: 2 orbital
(antibonding character,
localized on C)
B. Electronic structure of CO complexes
CO is not only a donor, but also a acceptor.
+
: C
: C
O:
O:
-donation
-backdonation
How many bonds can a CO form with a transition metal ion?
M
+ C O:
C O:
empty
M
M C O
+ C O:
empty
M C O
C O:
M C O
Depending on the metal and other ligands, the
nature of the CO ligand in LnM-CO can vary.
- If L are good acids or the complex is cationic,
then -donation will be more important (A)
- If the L are -donors or the complex is anionic, then
the metal will be a strong -donor. (C)
Q2. In metal complexes, we usually observed
:C O:
not
why?
Electronegativity consideration:
:C O:
2
3
O 3
1
C
1
In term of orbital interaction:
O
1
M C O
C O M
C O
C O
C O
C O
better overlap
M
M
O
2
-donation
Effect of complexion
M C
M C
:C O
-backdonation
O
M
M
+
M
donation backdonation overall
d(M-C)
d(C-O)
(CO)
e- density on C
e- density on O
Expected reactivity:
M
Nu-
C O
E+
C. Preparation of CO complexes
(1) From CO
Metal + CO
Ni + 4 CO
OC
OC
Fe + 5 CO
Ni
CO
CO
Fe(CO)5
18e
18e
Colorless liquid,
b. p. = 34 oC
yellow liquid,
b. p. = 103 oC
Metal Salts + reducing agent + CO ==> 18e complexes
Typical reducing agents: Na, Al, H2, AlR3, CO ...
OC
CrCl3 + Al + 6 CO
OC
CO
Cr
CO
VCl3 + Na + CO
Cl
Cl
W
Cl
Cl
CO
+ AlEt3 + CO
OC
OC
18e
18e
NaV(CO)6
Cl
Cl
CO
CO
W
CO
CO 18e
CO
O
C
OC Co
OC
OC
CoCO3 + H2 + CO
O
C
CO
Co
CO
CO
OC
Mn(OAc)2 + CO + AlEt3
CO OC CO
OC Mn
Mn CO
OC
CO OC CO
Unsaturated compounds + CO
Ph3P
CO
Ir PPh3 + CO
Cl
16 e
CO
Cl
Ir
CO
PPh3
PPh3
18 e
(2) From a reactive organic carbonyl compound.
Example 1.
Ph3P
+
C
R
Cl
Ph3P
Cl
Cl
+ RCl
Mechanism?
O
O
Ph3P
Cl
CO
Rh PPh3
PPh3
Rh PPh3
PPh3
C
Rh PPh3 +
R
Cl
Ph3P
Rh
Cl
16e
O
Ph3P
Cl
Ph3P
Cl
Cl
Ph3P
16e
CO
Rh PPh3
16e
Cl
CO
PPh3
Rh
Cl
R
PPh3
PPh3
18e
PPh3
Rh R
Cl
18e
Example 2.
IrCl3 + PPh3 + CH 3CH2OH
Mechanism?
Ph3P
Cl
CO
Ir PPh3
D. Structures of M-CO compounds.
The three principal coordination modes of CO:
O
OC
Ni
OC
CO
OC
CO
Cr
CO OC
CO
CO
OC
OC
Ru
OC
Ru
OC
CO
CO
CO
O O
CC
OC
C
M
CO
CO
CO
CO
CO
Ru CO
Fe
OC
OC
CO
Fe
C
O
CO
CO
CO
OC
C
M
M
M
2-complexes
OC
CO
Rh6(CO)16
Rh(CO)2
3-complexes
Other less common coordination modes
O
SemibridingCO
Fe
C
M
O
C
Fe
Fe
2.07
1.86 O
Fe3(CO)12
O
C
M
Ph2P
OC
Mn
OC
Ph2P
bridgeCO
O
C
M
O
C
M
O
PPh2
Mn
CO
PPh2
CO
Mn2(dppm)2(CO)5
C
M
M
M = CpNb(CO)2
E. Characterization of M-CO compounds
C NMR.
13
O
M
(CO), ppm:
C O
150-220
C
M
230-280
IR: (CO), cm-1
C O M
C O
M
2143
M
M
O+
C M
M
M
1850-
1700-
1600-
2150
1860
1700
Molecular symmetry and IR bands.
C
Cl
O C Pt C O Cl Pt C O
Cl
Cl
B
A
O C
C O
How many IR bands due to (CO)?
Symmetric stretch
O
No change in dipole moment,
IR inactive
C
O
Change in dipole moment,
IR inactive
Unsymmetric stretch
O
M
O
Change in dipole moment,
IR inactive
C
O
C
O
Change in dipole moment,
IR inactive
C
M C O
For a given,
molecules, the
numbers of expected
IR bands can be
determined by group
theory. e.g.
formula
structure
point group
IR band
CO
M(CO)6
M(CO)5L
M(CO)4L2
CO
OC
M CO
OC
CO
L
CO
OC
M CO
OC
CO
L
CO
OC
M CO
OC
L
CO
L
OC
M L
OC
CO
Oh
C4h
D4h
C2v
C2v
C3v
M(CO)3L3
CO
L
M CO
OC
L
L
CO
L
M CO
L
CO
F. Reactions of metal carbonyls
LnM
E+
Nu-
oxidation
reduction substitution
(1) Substitution
OC
OC
CO
Cr
CO
CO
CH3CN
OC
CO
reflux
OC
CO
NCMe
OC
NCMe
NCMe
OC
Cr
useful starting material
OC
OC
CO
Cr
CO
CO
CO
OC
OC
CO
Cr
CO
CO
CO
NCMe
CO
Cr
NCMe
NCMe
not
(2) Nucleophilic attack on carbon
L nM
O + Nu
L nM
CO
OC
OC
CO LiMe
Mo CO
OC
CO
Mo
CO
CO
CO
CO
+ LiBHEt3
Nu
O- Li
E+
Nu
O E
LnM
CO CO
MeI
C
Me
OC
OC
CO
OC Fe
Ln M
CO CO
OC
OC Fe
CO
Li+
CO
CO
Mo
CO
Nu
O- Li
C
Me
Ph3
Re
CO
+ LiBHEt3
ON
O
C
OC
CO
Fe
CO
+ LiOH
CO
CO
OC
OC
CO
+
Mo C O + O NMe3
CO CO
OC
OC
CO
O
C
OC
Fe
CO
CO
CO
+
+ O NMe
+ PMe3
-Mo
CO
CO CO
O
OC Mo NMe3
+
O NMe3 CO2 OC CO
(3) Electrophilic attack at oxygen e.g
.
PR3
Cl
R3P
PR3
Re C O: + AlR3
PR3
PR3
Cl
R3P
PR3
Re C O:
AlR3
PR3
(4) Migratory insertion reactions
PMe3
CO
CH3
OC
OC
CO
Mn C O + PMe3
CO
OC
OC
Mn
CO
CH3
(4) Oxidative decarbonylation
OC
CO CO
CO
CO
CO CO
CO
+ X2
OC
CO
OC Fe
CO
CO
CO
I2
OC CO
OC CO OC CO
M = Mn, Tc, Re
X = H, Cl, Br, I
CO CO
+
I
OC Fe
OC CO
I-
CO I
I
-CO OC Fe
OC CO
2. Metal complexes of CO-like ligands
:C O: :C
N-R
:C
S:
:N O:
:N N:
A. Isocyanide complexes (metal isonitrile)
M C O
M C
N-R
(1) In terms of composition and structures, metal isonitriles
are very similar to metal carbonyls. e.g.
M(CO)6
M(CO)5
M2(CO)10
M(CNR)6
M(CNR)5
M2(CNR)10
M = Cr, Mo W Fe, Ru, Os
M(CO)4
M(CNR)4
Mn, Tc, Re Ni, Pd, Pt
(2) In terms of chemical properties, they are also very similar.
L nM
L nM C
O + Nu-
L nM
NR + Nu-
L nM
O
C
L nM
Nu
Nu
NR
NR
L nM
Nu
Nu
O
LnM
O + L'
LnM
L'
R
NR
LnM
R
C NR + L'
LnM
L'
LnM
O: + E+
LnM
E+
O:
e.g. AlBr3
LnM
C NR + E
+
L nM
E
C N
(3) Difference between CO and CN-R.
* Which one is a stronger donor, CO or CNR?
CN-R
* Which one is stronger acceptor, CO or CNR?
CO
* CN-R can form complexes with metals in higher oxidation
state.
[Pt(CO)4]2+ does not exist.
[Pt(CNR)4]2+ is stable.
L nM
* M-CNR complexes are
more reactive toward both
L nM
nucleophiles and
O: + ROH
N. R.
C NR + ROH
L nM
O
R
electrophiles.
R
In general
R
C N R
+ H-A
NHR
N H
M
C
A
L nM
NR
O+ H
R
L nM
N-
O+ H
R
Exercise. Provide the products for the following reactions.
Cl
Cl
Pt
C N Ph
+ EtOH
PEt3
R
N
C
R N C
Pt
C
N
R
2+
C N R + 4 HNMe2
B. CS complexes
CS unstable (more reactive); M-CS stable
Examples
Ph3P
Cl
CS
Rh
PPh3
+
Fe
OC
OC
Chemical properties of M-CS complexes:
Very similar to M-CNR complexes (More reactive than CO complexes).
CO CO
OC
OC
C S + HNR2
CO
CO CO
OC
OC
W
CO
+
C S + Me3O BF4
C. NO (nitrosyl) complexes
Lewis structure
NO
.
:N
NO+ (isoelectronic to CO)
..
O:
+
O:
:N
MO description
2
3
O 3
1
N
1
2
O
1
Bonding in M-NO.
How many e- can NO donate?
O
M
linear
bent
sp N
O
M
3e donor
sp2 N
1 e donor
Q1. What is the electron count for the following complexes?
O
R2 N
P
Co
P
R2
A
2+
R2
P
P
R2
O
R2 N
P
Co
P
R2
Cl
B
R2
P
P
R2
Q2. How could we differentiate linear or bent NO ?
O
M
linear
, (NO), cm-1
bent
1610-1830
1520-1720
Q3. Can we predict if a NO is linear to bent?
But, it is not always true. e.g.
O
Cl
Cl
PPh3
Co N
PPh3
18e
Cl
Cl
PPh3
Co N
PPh3
16e
O
O
N
Co
18e
O
PPh3
PPh3
O
O
N
Co
16e
PPh3
PPh3
Preparation of NO complexes
(1) From NO gas
Cr(CO)6 + excess NO -----> Cr(lin-NO)4 + 6 CO
Fe(CO)5 + excess NO -----> Fe(CO)2(NO)2 + 3 CO
Note: 2 NO for 3 CO. Why?
(2) From NOBF4, e.g.
OC
+ NOBF4 + MeCN
Cr
CO
CO
2+
2BF4-
O
MeCN
MeCN
18e
NCMe
Cr
NCMe
N
O 18e
+
Mo
CO
+ NOBF4
CO
18e
Mo
CO
18e
BF4-
NO
Note: 1 NO+ for 1 CO.
Some chemical properties of M-NO complexes
a. Line M-NO and bent M-NO interconversion
LnM
18e
O
LnM
16e
important in substitution reactions.
b. They are less reactive towards nucleophiles and electrophile than CO.
c. M-NO complexes can also undergo insertion reactions.
Co
+ PPh3
N
# VE = ?
Ph3P
Co
N
R
3. Phosphines as ligands
Phosphines are probably the most important organometallic ligands
because their steric and electronic properties can be easily modified.
A. Nature of M-PR3 bonds
PR3 can function as -donor and a acceptor.
M
:PR3
PR3
How do phosphines function as -acceptor?
Early belief.
M
M
PR3
However:
* No experimental evidence supports it.
* Theoretical calculation shows that d-p interaction is not important here.
Current belief:
The -accepting properties of PR3 is due to d(M) -> *(P-R).
..
X
Recall MO of
Y
N
Y
Y
3a1
z
y
x
(e.g. NH3)
M
P
H
H
M
2e
2p
2a1
a1
2s
1e
1a1
Phosphines, like amines, are
strong -donors. Unlike amines,
they are also -acceptors.
Evidences for d(M)->* (P-R) bonding.
Q1. If there is d(M)->*(P-R) bonding,
R
M
P-R bond becomes logner or shorter?
M-P bond becomes logner or shorter?
(MeO)3P
+
(3-C8H11)Fe
(MeO)3P a
(MeO)3P
OMe
P
OMe
OMe
(3-C8H11)Fe
d(P-O)a - d(P-O)b = - 0.021
d(M-P)a - d(M-P)b = - 0.015
longer
OMe
P
OMe
OMe
(MeO)3P
b shorter
As a result, the
backdonation
from metal to
PR3 plays a
Important role.
Q2. Trans-TiMe2(dmpe)2 is diamagnetic why?
P = Me2P
Me
z
P
P Ti P
P
Me
y
x
D4h
B. Electronic effect of substitutents in PR3
Q1. Consider the ligands PCl3, PPh3, PMePh2, PMe3.
What is the order of -donating ability ?
What is the order of accepting ability?
-donating ability:
accepting ability:
Electron-donating groups on P will
*increase -donating ability
*decrease accepting ability
*overall, increase the basicity of PR3
acceptor ability
PR3 P(NR2)3 < PAr3 < P(OR)3 < P(OAr)3 < PCl3 < CO PF3
Q2. Why is PF3 a stronger acceptor than PMe3?
*(P-C)
*(P-N)
*(P-O)
*(P-F)
P
C
N
O
F
Electron-withdrawing group X make the *(P-R) have lower
energy, thus increase the accepting ability.
Q3. Which of the following complexes would you expect to have the
lowest C-O stretching frequency?
(a) Ni(CO)4
(b) Ni(CO)3(PPh3)
(c) Ni(CO)3(PMe3)
(d) Ni(CO)3(PPhMe2)
The electronic parameter
The electron donating or withdrawing ability of phosphines can be correlated with the
CO stretching frequency of monophosphine metal carbonyls. While any metal
carbonyl can be used, LNi(CO)3 is used most commonly.
C. Steric influence of ligands.
PR3 Ligands have varying size, depending on R.
Tolman introduced the concept of cone angle to describe the size of
PR3.
R
R
R2
R
R3
2.28A
R1
P
2.28A
M
i=3
= 2/3 i/2
i=1
Can cone angle be larger than 180o ?
PR3
structure of R
P(OEt)3
o
cone angle )
O Et
109
PMe3
Me
118
PEt3
Et
132
PPh3
P(i-Pr)3
145
Me
Me
170
PCy3
P(i-Bu)3
Me
Me
Me
Me
Me
Me
P
M
182
194
P(o-C6H4Me)3
P(mesityl)3
160
212
Importance of cone angles.
* Cone angle determines the maximum number of ligands that can be
attached to a metal. e.g.
PCy3, P(i -Pr)3 ----> at most M(PR3)2 ( = 170o, 160o)
PPh3 --------> M(PPh3)3 or M(PPh3)4 (rare) ( = 145o)
PMe3 --------> M(PMe3)6 is possible. ( = 118o)
* Useful when steric effect is considered,
e.g. in substitution reaction rates
Phosphines tend to be sterically demanding, and thus steric effects dominate
coordination
- Bulky phosphines will tend to bind trans to one another
- The presence of several bulky phosphines will result in deviations from
ideal geometries.
Summary. Electronic ans steric
properties of typical phosphines.
Chelating phosphines
Chelating phosphines are widely used to control structure and reactivity.
Chelating diphosphines preferentially coordinate in cis fashion, while 2
monophosphines would adopt a trans geometry.
Natural Ligand Bite Angle (n): The ligand preferred P-M-P angle for a
chelating diphosphine. This can be determined from x-ray structures or by
molecular modeling. (Chem. Rev., 2000, 100, 2741-2769)
4. Substitution reactions
Introduction to substitution reactions
LnM-X + Y --------> LnM-Y + X
Types of substitution reactions:
LnM-X + Y- --------> LnM-Y + XLnM-X + :L' --------> LnM-L'+ + XLnM-L'+ + X--------> LnM-X + :L'
LnM-L' + L"-------> LnM-L" + :L'
2e ---> 2e
Examples:
Ti Cl
Cl
+ MeLi
Ti
OC
Fe
CO
CO
+ I2
OC
Fe
CO CO
CO
CO
I
CO
CO
CO
CO
I-
- CO
OC
Fe
CO CO
CO
Mn
+ LiCl
Me
CO
CO
Me
CO
+ PPh3
Ph3P
Mn(CO)4
Mn
CO
CO
CO
I
I
Me3P
Me3P
H
Ru
O
Cr
OC
CO
+
OC
Re
Me3P
PMe3 + PMe
3
O
Me3P
CO +
OC
OC
CO
PMe3
Ru
Me3P
CO
OC
H
O
O
CO
Cr
+ 2 CO
CO
+ PPh3/Me3NO
NO
PPh3
M CO + Me3NO
+
Ph3P
O
M C +
O-NMe3
Re
NO
PPh3
+ CO2 +
NMe3
Majormechanismsforsubstitutionreactions?
LnML'+L">LnML"+:L'
*Dissociativesubstitution
LnML'>LnM+L'
ratedeterminingstep
LnM+:L''>LnML"
*Associativesubstitution
LnML'+:L''>LnML'L"
ratedeterminingstep
LnML'L">LnML"+:L'
*Interchangemechanism
LnM-L' + L"
LnM
L'
LnM-L'' + L'
L"
Notes: Associative substitution undergoes an intermediate while
interchange mechanism undergoes a transition state.
A. Dissociative substitution
Q1. What is the most important feature for D mechanism?
LnM-L' ----------> LnM + L'
slow, rate determining step
LnM + :L'' --------> LnM-L"
fast
Q2. What types of complexes are likely to undergo
substitution reactions via D mechanism?
OC
OC
CO
CO
Cr
CO
18e
CO
CO
OC Fe
18e
CO
CO
CO
OC
Ni
OC
18e
CO
CO
Q3. Stereochemistry retained or lost?
Lt
M
Lt
+ L'
L
stereochemistry:
Lt
Lt
or
L'
retention
lost
Lt
L' ?
Lt
M
square pyramid
TBP
L'
L'
L'
Lt
Lt
M
M
L'
L'
[Link]? trans ligand
metal
Lt
M
+L
Lt
X
cis ligand
Li
+ Ld
X
leaving group
Q4A. Effect of metal. Consider the reactions below. Which one is fast?
(a) Ni(CO)4 + PPh3 -----> Ni(CO)3(PPh3) + CO
(b) Cr(CO)6 + PPh3 -----> Cr(CO)5(PPh3) + CO
(a). Ni(0), d10, no CFSE. Ni-CO bond is weaker.
* The substitution reactions of d3, d6 (low spin) octahedral complexes are
usually very slow.
Q4B. Consider the reactions below. Which one is fast?
(a) Fe(CO)5 + PPh3 -----> Fe(CO)4(PPh3) + CO
(b) [Fe(CO)5]- + PPh3 -----> [Fe(CO)4(PPh3)]- + CO
Q4C. Effect of leaving ligand. What is the likely product?
OC
OC
CO
W
CO
CO
N
OC
+ PPh 3
CO
CO or
OC
CO
Me
PPh3
OC
OC
CO
PPh3
CO
Me
2+
+
Fe
h
CH3CN
Fe
Me
N
N
C
Me
C
Me
+
or
Fe
Me
N
N
C
Me
C
Me
* Also chelating ligand
dissociate less readily
than monodentate
ligands.
Q4D. Effect of trans ligand. What is the likely product?
OC
OC
CO
Mo
CO
CO
PMe3
+ PMe3
Me3P
CO
OC
CO
PMe3
CO or
M
0
Mo
OC
PMe3
OC
PMe3
CO
CO
A
If bulky PR3 is used instead of PMe3, A may be favored due to steric
effect.
Q4E. Effect of spectator ligand (steric effect). Consider the reactions
below. Which one is fast?
(a) Ni(PPh3)4 + CO -----> Ni(CO)(PPh3)3 + PPh3
(b) Ni(PMe3)4 + CO -----> Ni(CO)(PMe3)3 + PMe3
(c) Ni(CO)(PMe3)3 + PMe3 --->Ni(CO)2(PMe3)2 + PMe3
B. Associative substitution
Q1. What is the most important feature for A mechanism?
LnM-L' + :L'' -------> LnML'L"
rate determining step
LnML'L" -------> LnM-L" + :L'
* Rate depends on both LnM-L' and L"
rate = K[LnM-L'][L"]
* S# < O
Q2. What types of complexes are likely to undergo
substitution reactions via A mechanism?
* 16e species normally undergo D mechanism.
L
Lt
Ld
Li
Li
Lt
L
16e
Ld
18e
-L
L
Lt
L
16e
Li
< 18 e complexes. e.g.
V(CO)6 + PPh3 -----------> V(CO)5(PPh3) + CO
17e
[V(CO)6]- + PPh3 -----------> [V(CO)5(PPh3)]- + CO
18e
slow
18e complexes that can rearrange to 16e species. e.g.
OC
OC
CO
CO
Mn
N O +L
CO
18e
OC
OC
OC
OC
L
Mn N
CO
18e
CO
Mn
CO
16e
- CO
N
O
OC
OC
L
Mn
CO
18e
N O
Other complexes capable of such rearrangement:
MLn
MLn
MLn
MLn
18e
16e
18e
16e
Q3. What affect reaction rates?
trans ligand
incoming ligand
metal
Lt
M
+L
X
cis ligand
Lt
M
X
leaving group
Li
+ Ld
Exercise 1. Consider the following associative substitution reactions.
Which one reacts faster, PMe3 or PPh3?
V(CO)6 + PR3 -----------> V(CO)5(PR3) + CO
PMe3, It is a better s donor, V-P bond is stronger.
Which one reacts faster, PCy3 or PPh3?
Exercise 2. 19e or 17e usually undergo substitution reactions fast than
18e complexes. Suggest a reason.
