Professional Documents
Culture Documents
C21J, 4 Lectures
Mohammed Bakir, Office #8
Introduction
Bonding
-acids
Metal Carbonyl Compounds
Organometallic Compounds
Preparation and reactions of organometallic
compounds.
Reference: Chapters 10
Textbook: B. Douglas, D. H. McDaniel, & J. J.
Alexander, Concepts & Models of Inorganic
Chemistry, 2nd edition, Wiley, New York
What is Organometallic?
Organometallic is the chemistry of M-C bond
formation and reactivity.
Although Zn-alkyls e.g. Zn(CH3)2 were
prepared by Frankland in 1827,
organometallic chemistry has undergone a
renaissance in the last 50 years due to the
importance of many organometallic
compounds in many important chemical
processes that include catalysis, sensors and
others.
Metal Carbonyl Compounds
-acid Ligands.
What are -acid ligands?
Ligands with a pair of electrons available
for donation to the metal center and
vacant orbital p, *, or d available for
accepting electron density from the metal.
e.g. CO, and PPh3 where Ph = C6H5.
2s
nb
2p
2s
nb
2s
1s
1s
1s
C
Full nb
nb (O)
1s
1s
Sketches of the M.O. for CO
+ -
C O x*) or y*
(
- +
+
x) or y
O (
C
-
-C + O-
+ C - - O +
nb) C
( nb) o
(
Metal Carbonyl Compounds
Requirements
Metal should be in low oxidation state 0, 1 or
2; i.e. electron rich.
Ligand should a -acceptor ligand, i.e. -
donor or electron acceptor through empty p,
* or d orbitals.
Bonding
Sequence of bonding
A pair of electrons is donated from the -
acid to the metal center
The excess electron density around the
metal center is donated back to the empty
orbitals on the ligand.
Synergic Bonding
- + + -
M + + M
C - O + C O
+ - - +
Stable V(CO)6-
Metal carbonyls
M = Cr, Mo, & W 3d4 4s2
M0 = 6 e-
6xCO = 12 e-
Total = 18 e-
Stable M(CO)6 stable
Mn, Tc, Re
M0 7
Need 11 e-
Possibilities
1. M(CO)5-
2. M(CO)6+
3. (CO)5M-M(CO)5 Metal metal bond donates
1e to each metal
Mn2(CO)10
Mn - Mn
CO
Co2(CO)8
CO CO CO All CO terminal
Bridging C=O)
OC Co - Co CO
C=O
C=O
CO
CO CO
CO
OC Co - Co CO
CO CO
CO
Metal Carbonyls
C=O
C
M M M M
C
C=O
O
I.R. (C
O) ~ 2150 -1850 cm-1
(C=O) -1850-1750 cm-1
(C-O) ~ <1600 cm-1
fac-Re(CO)3(dpk.oxim e)Cl and fac-Re(CO)3(dpk)Cl
, heptane, -40
h
M(CO)5 M2(CO)9
1-bridging COs
M= Ru, Os
M3(CO)12
Higher nuclearity
3M(CO)5 M3(CO)12
M = Fe, Ru, Os
3 M = 24 e-
12 CO = 24 e-
Need 3x18 = 54e- for EAN
6e- short, then need 3 (M-M) bonds
M4(CO)12
M(CO)3
4xM = 36 e-
12 CO = 24 e-
(CO) M M(CO)3
Total = 60 e- 3
M(CO)2
Rh6(CO)16
6xRh = 54
16xCO = 32
Total 86
3Os(CO)5 Os3 (CO)12
h
2Fe(CO)5 Fe2(CO)9
Substituted Carbonyls & Carbonylate Anions
P:
:C N R
PPh3
Metal Carbonyl Reactions 2
2. Oxidation
Mn02(CO)10 + Cl2 MnI(CO)5Cl
Fe0(CO)5 + Br2 FeII(CO)4Br2
Co02(CO)8 + H2 H+[Co(CO)4]-
Substitution Reactions 3
3. Rearrangements
~90 C
2RhCl3 + 4 CO [Rh(CO)2(-Cl)]2 + 2Cl2
OC Cl: CO
Rh Rh
OC :Cl CO
2Mn(CO)5Cl W
+CO, pressure
Mn2(CO)8(-Br2)
[Rh(CO)2(-Cl)] + 2 PPh3
trans-Rh(PPh3)2(CO)Cl + CO
Carbonylate Anions
Synthesis
Reaction of metal carbonyls with base.
e.g.
Mn(CO)5- + Re(CO)5Cl
(CO)5Re-Mn(CO)5 + Cl-
Re(CO)5Cl + 2 KCN
K[Re(CO)4(CN)2] + KCl + 2 CO
Reactions with alky, acyl halides
Re(CO)5- + CH3I (CO)5Re-CH3 + I-
Mn(CO)5- + CH3C(=O)Cl
(CO)5Mn-C(=O)CH3 + Cl-
Protonation of Carbonylate anions
Mn(CO)5- + H+ H-Re(CO)5
Fe(CO)4-- + H+ H-Fe(CO)4-
H-Fe(CO)4- + H+ H2-Fe(CO)4
Oxidation States
Always consider the metal in its zero
oxidation state.
e.g.
H-Mn(CO)5
Br-Mn(CO)5
CH3-Mn(CO)5
Mn in oxidation state of zero,
H, CH3, Br all donate 1 e-.
Reactivity of polynuclear Carbonyls
1 CO 2 e-; if 1 CO is removed then
you need to replace it with two 1 e-
donors such as H, CH3, Br
e.g. Os3(CO)12
Os3(CO)12 + H2 H2Os3(CO)10
W
H2Os3(CO)11
Bonding
CO
H H
H H
Os
H2 + CO
Os3(CO)12 H2Os3(CO)10 H2Os3(CO)11
- CO
Bonding
Cl2
Os3(CO)12 Os3(CO)10Cl2
CO
Cl Cl
Cl Cl Cl Cl
Os
2 e- donor 3 e- donor
Bonding
2 Mn(CO)5Br Mn2(CO)8Br2 + 2 CO
Br
Br Kinetic product
Mn - Mn
Mn = Mn Br
Br
Br
Mn Mn
Br
Thermodymanic product Observed
Nitric Oxide Ligand
NO has a very similar M.O. diagram to
that of CO, except that it contains one
extra electron in the * orbital.
. 3 e- are donated
to the M.O. scheme
M O:
:N of the complex by NO.
In this case L-N-O bond
~ 170 -180 .
NO is 3 e- donor;
NO+ is 2 e- donor
i.e. NO+ CO, i.e. isoelectronic
Compounds of NO
Co(CO)4NO; Mn(CO)4NO; Fe(CO)2(NO)2.
EAN ? Check.
metallocyclopropane
M M
Acetylene
As in the case of olefins, acetylene can use
one of its p-bonds or both to coordinate to
metal atoms. Note each -bond is 2e-
donor.
H2C = CH2
H2C CH2
M M
e.g.
Co2(CO)8 + HC CH Co2(CO)6(ac)
HC - CH
M-M
Conjugated Olefin Systems
Ferrocene
FeCl2 + 2 NaCp FeCp2
= Cp-
- is 5e- donor
Fe
5-Cp
Pentahapto
Staggered=sandwich
Reactions of Cp-compounds
With Organometallics
Li
CO2H
BunLi
Fe CO2/H+
Fe Fe
Reactions of Cp-compounds
THF
Mo(CO)6 + NaCp Cp-Mo(CO)3
+H+ +CH3I
5-Cp-MoH(CO)3 5-Cp-Mo(CH3)(CO)3
, 2
[5-Cp-Mo(CO)3]2 [5-Cp-Mo(CO)2]2
-2CO
Cp
Mo Mo
Cp
Reactions of Cp-compounds
Nucleophilic Addition
CoCp2 + CH3Br Co(5-Cp)(4-C5H5R) + Br-
Co
H R
Reactions of Cp-compounds
Addition reactions [2 + 2] cycloaddition
NiCp2 + F2C=CF2 Ni(5-Cp)(3-C5H3C2F4)
Ni
3-
F
F F
F
Other systems
Allyls
NaMn(CO)5 + H2C=CH-CH2Br
Mn(CO)5(1-CH2-CH=CH2)
Mn(CO)4(3-CH2-CH=CH2)
(CO)4
M
Mn(CO)4
Other systems
+ Fe(CO)5 4-
Fe(CO)3
H H
H H
4-
+ Fe(CO)5
Fe(CO)3
Reactions H H
H H
4-
+ Fe(CO)5
Fe(CO)3
O - CO
Cp C CO
CpFeH(CO)2
Fe - Fe -H2
5-
OC C Cp
O
Other ring systems
Cyclobutadiene 4-
H
Cl
Fe2(CO)9 + 2 + 3 CO + 2Cl2
Cl
H
Fe(CO)3
CH3COCl/AlCl3
COCH3
Fe(CO)3
Other ring systems
Benzene
Et2O/H2O
PhMgBr + 2 CrCl3 [Cr(PhH)2+]
+ e-
6-
Cr(CO)6
Cr(CO)3 Cr