Outline: General Properties of Organometallic Complexes
Outline: General Properties of Organometallic Complexes
Outline: General Properties of Organometallic Complexes
Outline
1.
2.
3.
4.
5.
6.
7.
References
1. The Organometallic Chemistry of the Transition Metals, Robert H. Crabtree,
3rd Edition, 2001, Chapter 1-2.
2. Organotransition Metal Chemistry, Akio Yamamoto, 1986. Chapter 1-4.
3. Organometallic Chemistry, G. O. Spessard, G. L. Miessler, Prentice-Hall:
New Jersey, 1997, Chapter 1 3.
H3N:
Co
H3N:
..
NH3
3+
3+
NH3
:NH3
:NH3
or
H3N
H3N
Co
NH3
NH3
NH3
Ligands: a molecule or ion that has at least one electron pair that can be
donated.
The electron pair can be: lone pair, p-bonding electron pair, or
s-bonding electron pair.
Classification of ligands
A). Based on nature of the donating electron pairs, ligands may be
classified as Lone pair donor, p-bonding electron pair donors, s-bonding
electron pair donors.
H3N:
H3N:
..
..
H2O: H2O:
H H
M
M
H
SiR 3
M
:L
H3N:
..
..
NH2-CH2-CH2-NH2 (en)
In terms of bonding:
M
empty
:CO :PR3
..
R-O.. :
..
Cl :
..
L or M
M L
filled
L ligand
Note:
Ligands that donate
electron pairs to form M-L
M
L ligand
L ligand
Bonding
e.g. OR.. :
R-O
..
(a)
M
OR-
(a)
M
.. :
R-O
..
OR- or M
empty filled
R-O
(b)
M
R-O
OROR-
OR
OR
OR
Ligands that donate electrons to metal to form p bond are called p donor
How many p bonds can an OR form with a transition metal ion?
(a)
:C O:
C O:
+ C O:
C O:
(b)
M
C O:
empty
accept e- to form p bond (dppp back bonding)
Ligands that accepting electrons from metal to form p bond are called
p acceptor.
How many p bonds can a CO form with a transition metal ion?
(a)
:C O:
C O:
+ C O:
C O:
C O:
empty
TWO
+ C O:
C O:
empty
M C O
M C O
M C O
lone pair
donor
strong
p acceptor
weak
p bonding
CO, PF3
NH3, HCH3-
strong
p donor
Cl-, OR-
4s
2.38
1.99
a)
OC
OC
Mo
2p
CH3
3s
2p
C
O 3s
(anti-bonding)
CO
1p
b)
IR, (CO)
:C
2149 cm-1
H3B C
2178 cm-1
CO CO
OC Cr
CO
OC
CO
1p
2s
1s
2s
2000 cm-1
:C
:C
M C
Explanation?
M
+
M
t-Bu
t-Bu O O
Mo
t-Bu
O O t-Bu
120o
Mo
O O
O
O
Tp
180o
O
Nb
O
Tp
Tp = trypticyl
H2C
CH2
M
HC
CH
M
H
H H
C
M
M
H
C
M
d
---> p (C
2H4)
1. e - fromp(C2H4) --->s (M) 2. e - from p(M)
Hapticity of ligands:
A ligand may have more than one way to bond to a metal center, e.g.
CH
CH2
CH2
or
M
H M
M H
H
H
H
H
(Cp)
H
H
(h -C3H5)M
H
(h-H2)M
CH2
Ag+
CH2
(h-C2H4)M
(h-C6H6)M
(h-C6H6)Ag+
(h-C6H6)M
Fe(CO)3
O
CH3
Ru
MeO
Fe(CO)3
Cl
Cl
M
M
2-Cl
H
M
H
h
C
M
H
M
B
H
h4
2-OR
M
3
3-Cl
H
B
H
B
M
h2
3-CO
H
M
H
M
H H
M
h3
h -H2
OC
OC
PR3
CO
H
W
H
PR3
h -H-SiR3
SiR3
Mn H
OC
OC R3Si
Cl
agostic C-H
H
C
or M
H
C
Me2P
Me2P
CH2
Ti
Cl
Cl
CH2
Is H2 a p donor or a p acceptor?
M
s-bonding
M
p-bonding
Further Notes:
* Relative basicity of electron pairs:
lone pairs > p bonding electron pairs > s bonding electron pairs
* Therefore usual order of binding ability:
lone pair donor > p bonding electron pair donor > s bonding electron pair donor.
Consequence:
CH2
:PR3
CH2
CH2
H
M PR3
M
M
CH2
H
H
CH2
H
CH
R
H
C O
C
R
H
low oxidation state M
O
C H
R
* Hard ligands tend to form stable complexes with hard metal ions,
(usually those at high oxidation state, e.g. Al3+, Fe3+, Cu2+, Ti4+, Pt(IV)).
* Soft ligands tend to form stable complexes with soft metal ions,
(usually those at low oxidation state, e.g. Mn(I), Co(I), Fe(II), Pt(II),
Pt(0) .......)
Examples:
AlF63-, Ti(OR)4 are very stable complexes, but Pt(0)--F, Pt(0)--OR,
W(0)--F are very rare.
Cl
Cl
Pt
Pt(IV)
Cl
stable
very rare
2).
(NH3)5OsII
2+
NH2
- e-
3+
(NH3)5OsIII
slow
III
(NH3)5Os
NH2
3+
MXL5
MX2(L2)
MXL(LX)
B
H M
M
3
h
H
4
OC
Fe
Ni
OC
CO
OC
CO
OC
OC
CO
CO
10 + 4x2 = 18
Cr
CO
CO
8 + 5x2 = 18
CO
6 + 6x2 = 18
Why 18?
e.g.
Fe
2C5H5
2 x 5e
Fe
8e
18e
H
CO
OC Cr CO
OC
CO
5 CO
H
Cr
1-
5 x2e
1e
6e
1e
18e
Ionic model : Metal complexes are formed from Mn+ + L + X# VE = valence e- of Mn+ + e- from ligands
2 C5H5Fe
Fe2+
H
2 x 6e
6e
CO
OC
OC
18e
Cr
CO
CO
5 CO
5 x 2e
HCr
2e
6e
18e
Exercise:
Determine the valence electron count of the following complexes.
CO
OC
Mn
CO
OC
CO
CO
CO
Mn
OC
OC
OC
OC
Mn
CO OC CO
O
C
OC
CO
CO
Fe
O
C
CO
Fe
C
O
CO
CO
CO
Cl
Cl
Rh
Rh
Cl
Fe(CO)3
Cl
O
CH3
Fe(CO)3
O
CH3
Rh
Rh
MeO
Fe(CO3
Cr
Ru
Mn
CO
OC
OC
Fe
OC
OC
CO
W
CO
CO
Rh
Rh
OC
Ph2
P
(CO)3(PPh3)Fe
O
N
Co
Co
N
O
Ir(CO)2(PPh3)
CO
OC
OC
CO
H
Cr
CO
CO
CO
Cr
OC
CO
CO
H
R3P Ru
R3P
PR3
H
B
R3P Ru
H
R3P
PR3
H
B
NMe3
H
Additional exercise
PPh3
Ir
OC
CO
BPh3
Ir
OC
CO
N
Ir
OC
CO
[Cu(NH3)6]2+ (21e)
Pt(PCy3)2 (14e)
RhCl(PPh3)3 (16e)
IF7
(24e),
Cp2Be (12e),
SbF6-
(22e)
Lu Me
U
U: 7s25f36d1
Lu: 6s24f146d1
2x8+6 = 22e
2x5+1+17 = 28e
Class
18e rule
not obey
II
....16, 17, 18
not obey
III
18
obey
n(VE) = 18 ~ 22
n(d)
n(VE)
TiF62-
12
VCl62-
13
V(C2O4)33-
14
Cr(NCS)63-
15
Mn(CN)63-
16
Fe(C2O4)33-
17
Co(NH3)63+
18
Co(H2O)62+
19
Ni(en)32+
20
Cu(NH3)62+
21
Zn(en)32+
10
22
n(VE) 18
n(d)
0
0
1
2
3
4
4
5
6
8
n(VE)
12
12
13
14
15
16
16
17
18
16
Metals in relatively
High oxidation state
Class III
n(VE) = 18
n(d)
n(VE)
V(CO)6-
18
CpMn(CO)3
18
Fe(CN)64-
18
Fe(CO)42-
10
18
Explanation:
L
Take Oh
L
L
L
L
t1u*
as an example
np
===>
eg* (antibonding):
t2g (nonbonding):
a1g, t1u, eg (bonding):
Total e-:
Minimum # of e-:
Maximum # of e-:
0 - 4e
0 6e
12e
a1g*
eg*
ns
(n-1)d
metal
orbitals
(a1g+eg+t1u)
t2g
Ligand
orbitals
(a1g+eg+t1u)
3d metal complexes with weak field ligands e.g. H2O, NH3 and
Cl- belong to this class (class I).
t1u*
np
0e
0 6e
12e
a1g*
eg*
ns
(n-1)d
metal
orbitals
(a1g+eg+t1u)
t2g
Ligand
orbitals
(a1g+eg+t1u)
np
t1u*
t1u*
a1g*
a1g*
np
p*
eg *
ns
(n-1)d
metal
orbitals
t2g*
eg *
(a1g+eg+t1u)
t2g
Ligand
orbitals
ns
(n-1)d
D
t2g
metal
orbitals
(a1g+eg+t1u)
(a1g+eg+t1u)
Ligand
orbitals
a1g+eg+t1u
0e
6e
12 e
Since
organometallic
compounds
usually have pacceptors, D is
large and t2g are
bonding MOs.
They usually
have 18e valence
electrons (class
III).
Note, just like the octet rule, the 18-electron rule is not an
absolute requirement. There are many exceptions.
d8 metals:
The d8 metals (groups 8 - 11) have a
tendency to form square-planar 16
electron complexes.
2eu
a2u
eu
L
L
L
L
1a2u
2b1g
a1g
s
eg
3a1g
2a1g
d
1eg+1b2g
b2g
b1g
1b1g
a1g
1eu
1a1g
The rule is
particularly useful for
Groups 6-8
16 e- Compounds
14 e- Compounds
WMe6
OC
OC
PPh3
Cl
Os
Cl
PPh3
H
H
R3P
PR3
Fe
H
H
PR3
Problems with O. S. :
a) Ambiguous oxidation states
(Ph3P)2Pt
(Ph3P)2Pt
Pt(0)
Pt(II)
PPh3
OC
OC
PPh3
CH2
Os
O
PPh3
Fe(0)
Os
CH2
O
PPh3
Os(II)
Os(0)
Fe(CO)3
OC
OC
or
Fe(CO)3
Fe(II)
or
Fe(CO)3
Fe(IV)
Another example
H
W
H
P
H
H
P P
(a)
H
W
H
P
H
H
P P
(b)
H
W
H
P
H
H
P P
(c)
Cl
H3N
H3N
Cl
Co
ReH92-
NH3
NH3
six-coordinated
9-coordinated
Polydentate ligands:
C.N. = # of atoms bound to metal
= # of electron pairs involved in M-L s bonds.
# of L present
Ph2
P
CH3
Co
P
Ph2
Cl
4-coordinated
Ph2P
H
Ph3P
Ir
PPh3
Cl
6-coordinated
Fe
Fe
CO
CO
OC
# of L
C.N. = 1
C.N. = 1 + 3
Fe
Fe
OC
# of M-L
C.N. = 5
CO
CO
C.N. = 4 + 3
Fe
Fe
CO
OC
CO
C.N. = 3
C.N. = 2 + 3
Fe
OC
OC
+
M
C.N.
d6
prefer
octahedral
d8
prefer
square planar
prefer
tetrahedral
geometrical structure
C.N.
d6
prefer
octahedral
d8
prefer
square planar
prefer
tetrahedral
geometrical structure
linear
Mn(CH2SiMe3)2
trigonal
Al(mesityl)3
d8
T-shape
Rh(PPh3)3+
square planar
RhCl(CO)(PPh3)2
tetrahedron
Ni(CO)4
d8
Trigonal
bipyramidal
square
pyramidal
Fe(CO)5
d8,, d6
Co(CNPh)52+
d6,, d7
(benzonitrile)
Octahedron
trigonal
prism
Mo(CO)6
WMe6
d6,, d3
d0
6. Effect of complexation
M-L:
Complexation of L on M may cause:
* the change of electron density distribution on L
* new reactivity of L: unreactive ==> reactive
CH2
+ Nu-
N. R.
Examples:
but,
OC
OC
Fe +
+ ROC
OC
Fe
R
Another example,
H
H
E
H
H
H E
+
H
H
-H
E
H
NuN. R.
+
but,
H
H
NaBH4
Mn
OC
CO
CO
E+
(H-)
Mn
OC
CO
CO
N. R.
increase
decrease
N:
:C
=0
unreactive
O:
=0
Upon complexation
M
s-donation
M
:N
N:
N:
O:
+
:C
O:
p- backdonation
M
-N
C
C
N
-
Nu
overall
E+
Nu-
E+
1) Electronegativity differences:
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
1.3
1.5
1.6
1.6
1.6
1.8
1.9
1.9
1.9
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
1.2
1.3
1.6
2.1
1.9
2.2
2.3
2.2
1.9
La
Hf
Ta
Re
Os
Ir
Pt
Au
1.1
1.3
1.5
2.3
1.9
2.2
2.2
2.3
2.5
Late transition metals are more electronegative, thus they prefer lower
oxidation states (i.e., Rh(I) compared to Rh(III)).
decrease
increase
Fe(II)
stable
Ti(IV) stable
Os(VIII) stable
(2)
(a)
(3)
Fe
Ru
Os
Ti2+
(b) Fe2+
(c) Ni2+
(d) Zn2+
b) Cr(CO)6
W(CO)6
2000
1998
Effects of changing net ionic charge, ligands, and metal on the p basicity of a metal
carbonyl, as measured by (CO) values (cm-1) of the highest frequency band in the IR
spectrum
Changing Metal
V(CO)6
Cr(CO)6
Mn2(CO)10
Fe(CO)5
Co2(CO)8
Ni(CO)4
1976
2000
2000
2023
2044
2057
[V(CO)6 ]-
Cr(CO)6
[Mn(CO)6 ]+
[Fe(CO)6 ]2+
1747
1860
2000
2090
2204
[(MeNH2)Mn(CO)5 ]+
[(en)Mn(CO)4 ]+
[(tren)Mn(CO)3 ]+
2090
2043
2000
1960
H
P
P
H H
P
H
Fe
P
P
Ru
H
H H
P
H
H
P
P
H
P
Os
H
P
P
Os
H H
why not
H
M
s(H2)
H s*(H2)
M
H
P
H?
cyclopentadienyl
5e-;
therefore ferrocene (Cp2Fe) is 10 + 8 = 18.
* CO The carbonyl ligand
* PR3 The phosphines, where R is, for example
CH3 or -C6H5 (trimethyl phosphine and
triphenylphosphine).
*Ethylenes, butadiene, cyclooctadiene,
cycopentadienyl anion
butadiene