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Organometallic Chemistry

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

MO E-L Diagram for CO 1s O


M.O. Diagram for CO

Empty LUMO

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
+ - - +

LigandMetal bonding Metal ligand -back bonding


(one of a mutual is shown)

The back donation to the * orbitals should strongly


O.
affect the bond order of C
IR data can be correlated C-O bond order.
-acid Ligands

 Examples of 2-es donors & have empty orbitals


of -symmetry include isocyanides CNR and
carbenes :C(X)(Y) have empty 2pz orbital.
 -acids without C, NO+ (isoelectronic with CO),
:phosphines PR3 , arsines AsR3, stibenes SbR3,
bipyridine (bipy) and phenanthroline (Phen)
 Bipy & phen possess * orbital molecular
plane.
The Effective Atomic # Rule or
the 18e- Rule
 The rule predicts the stability of organometallic
compounds and simply states that stability is
attained or gained when all of the bonding and
non-bonding orbitals are occupied.
 The rule is useful in predicting the stoichiometry
of stable species and also reactivity patterns.
 CO donates 2e- to the system from the nb
orbitals on C.
Metal Carbonyl Compounds

 M-COs are important for their rich


properties and applications in many
industrial processes that include catalysis,
medical diagnostics and molecular
sensors.
 Mond Pprocess, 1890
 Ni(CO)4 Ni0 + 4CO
 Fe(CO)5 Fe0 + 5CO
Mononuclear Metal Carbonyls
 M(CO)x hydrophobic (lacking affinity for
water, i.e. water insoluble), volatile, soluble
in non-polar solvents.
 e.g. V(CO)6 Oh
Cr(CO)6 Oh
Mo(CO)6 Oh
W(CO)6 Oh
Fe(CO)5 tbp
Ru(CO)5 tbp
Ni(CO)4 Td
Mononuclear Metal Carbonyls
 Stable homoleptic carbonyls of transition metal
elements can be predicted using the EAN rule.
 Vanadium- 23V 1s2 2s22p6 3s2sp63d3 4s2
 V0 5 e-
 6xCO 12 e-
 1x1e- 1e-
 Total 18e-

 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

3400 3000 2600 2200 1800 1400 1000 600


-1
Wavenumber, cm
M2(CO)9
, CH3COOH
h
 Fe(CO)5 Fe2(CO)9
3-bridging COs (D3d)

, 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


 Need 4x18 = 72 e- M(CO)3


 need 6(M-M) bonds
M(CO)3

= bridging CO (CO)2M M(CO)2

M(CO)2
Rh6(CO)16
 6xRh = 54
 16xCO = 32
 Total 86

 6x18 = 108, then


need 22 electrons, i.e.
11 M-M bonds
Preparation of metal carbonyl Compounds
 Two procedures are used
 Direct reaction of a metal with CO
e.g. Fe(CO)5 and Ni(CO)4.
Fe + xs. CO Fe(CO)5
Ni + xs. CO Ni(CO)4
Note only Ni & Fe are prepared this way, xs.
excess.
 Reductive Carbonylation of metal salts using a
reducting agent or CO as a reducing agent.
e.g.
Reductive Carbonylation
 2Co(H2O)4(O2CCH3)2 + 8 (CH3CO)2O + 8 CO + 2H2
Co2(CO)8 + 20CH3CO2H
H2 is the reducing agent
 CoCO3 + H2 + 8 CO Co2 (CO)8 + 2CO2 + 2H2O
H2 is the reducing agent
 CrCl3 + Al + 6 CO Cr (CO)6
Al is the reducing agent

 VCl3 + Na(xs) + CO Na[V (CO)6]

 Re2O7 + 17 CO Re2 (CO)10 + 7 CO2


CO is the reducing agent
Polynuclear Carbonyls
 Higher carbonyls can be prepared
from the thermolysis or photolysis of
lower carbonyls
 3OsO4 + CO(xs) Os3(CO)12 + 12 CO2


 3Os(CO)5 Os3 (CO)12

h


 2Fe(CO)5 Fe2(CO)9
Substituted Carbonyls & Carbonylate Anions

 The carbonyl group in metal carbonyls are


labile and can be replaced with of other
ligands.
 The EAN role can be used to predict the
stability of the substitution product.
 e.g.
 Cr(CO)6 + CNR Cr(CO)5(CNPh) + CO
 Ir4(CO)12 + 2 PPh3 Ir4(CO)10(PPh3)2 + 2 CO
 Mo(CO)6 + Br- Mo(CO)5Br - + CO
Lewis Bases & # of valence es

 H-, X-, NCS-, CN- where X = halide = 2e- donor


 CO, CNR, NO+, PR3, P(OR)3, AsR3, NR3, SbR3, SR2,
:CXY
= 2 e- donor ligands
 R-, C(O)R-, Ar- = 2e- donor
ligands
 NO = 3e- donor Ligand
Metal Carbonyls Reactions 1
1. Direct Substitution
 2 e- 1 CO
 e.g.

 Cr(CO)6 + CNPh Cr(CO)5(CNPh) + CO


 Ir4(CO)12 + 2 PPh3 Ir4(CO)10(PPh3)2 + 2 CO
 Mo(CO)6 + Br- Mo(CO)5Br - + CO

P:
:C N R

Triphenylphosphine Isonitrile, R = Aryl or alkyl

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

Bridging chloride in this case is 3 e- donor,


explain? And predict if EAN is satisfied!
Reactivity of Organometallics
, -CO

 2Mn(CO)5Cl W
+CO, pressure
Mn2(CO)8(-Br2)

 Re2(CO)10 + Cl2 Re2(CO)8(-Cl2)

 [Rh(CO)2(-Cl)] + 2 PPh3
trans-Rh(PPh3)2(CO)Cl + CO
Carbonylate Anions
 Synthesis
 Reaction of metal carbonyls with base.

 e.g.

13Mn2(CO)10 + 40 OH- Mn(CO)5- + 2


Mn2+ + 20 H2O
Fe2(CO)9 + 4 OH- Fe2(CO)82- + CO32- +
20 H2O
Co2(CO)8 + 5 RNC [CoI(CNR)5]+ [Co-
I(CNR) ]- + 4CO
4
Reaction of Metal Carbonyls with a reducing agent
NH3(l)
 Fe(CO)5 + 2 Na Na2Fe(CO)4 + CO
THF
 Cr(CO)6 + Na/Hg Na2[Cr(CO)5] + CO
NH3(l)
 Cr(CO)6 + NaBH4 Na2[Cr(CO)5] + CO
THF
 Co2(CO)8 + 2Li[HB(C2H5)3]
Li [Co(CO)4] + B(C2H5)3 + H2
THF
 Mn2(CO)10 + 2KH KMn(CO)5 + H2
Reactions of Metal Carbonyls with Anions

 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.

 Bent M-NO, with M-N-O bond angle of 110-


120, then NO is 1 e- donor.
..
NO
M
Bonding of Organic Ligands to Metals
 Olifin Compounds
 Zeises Salt

K2PtCl4 + H2C=CH2 K[PtCl3(H2C=CH2)]


The bonding is best described by the Dewer-Chatt
Mode. The olefin here is a total of 2 e- donor to
the metal center.
H2C CH2
H2C=CH2

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

Note: this type of bonding is not common


Acetylene (ac) Bonding
 Bridging acetylene bonding is more common

 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