CHAPTER 5

Organometallic
Chemistry
 Advanced Organic Chemistry
5 1 INTRODUCTION
5-1

I. Organometallic chemistry timeline

 1827 Zeise's salt is the first platinum-olefin
complex: K[PtCl3(C2H4)]H2O Zeise's salt

 1863 C. Friedel & J. Crafts prepare

organochlorosilanes
 1890 L. Mond discovers Nickel carbonyl
 1899 Introduction of Grignard reaction
 1900 P. Sabatier works on hydrogenation
organic compounds with metal catalysts.
Hydrogenation of fats
 1909 P. Ehrlich introduces Salvarsan for
the treatment of syphilis, an early arsenic
based organometallic compound. Salvarsan
S l 2

撒尔佛散
• 1912 Nobel Prize: Victor Grignard and Paul
Sabatier
• 1930 Henry Gilman works on lithium
cuprates
RX + 2Li  RLi + LiX
• 1951 Ferrocene is discovered
• 1963 Nobel p prize for K. Ziegler
g and G. Natta
on Ziegler-Natta catalyst Ferrocene
• 1965 Discovery of cyclobutadieneiron
tricarbonyl (C4H4)Fe(CO)3
tricarbonyl,
• 1968 Heck reaction
• 1973 Nobel prize G. Wilkinson and E. O.
Fischer on sandwich compounds
• 2005 Nobel prize Y. Chauvin, R. Grubbs, and
R
R. Schrock on metalmetal-catalyzed
catalyzed alkene
metathesis
• 2010 Nobel prize Richard F. Heck, Ei-ichi
N i hi Akira
Negishi, Aki Suzuki.
S ki "for
"f palladium-catalyzed
ll di t l d (C4H4)Fe(CO)3 3
cross couplings in organic synthesis"
II. DEFINITION
Organometallic compounds (metal organyls, organometallics) are
defined as materials which possess direct, more or less polar
bonds M+— C- between metal and carbon atoms. In addition to
the traditional metals, lanthanides, actinides, and semimetals,
elements such as boron, silicon, arsenic, and selenium are
considered to form organometallic compounds, e.g. organoborane
compounds such as triethylborane (Et3B).
Organometallic chemistry is the study of organometallic compounds.
Since many compounds without such bonds are chemically
similar, an alternative may be compounds containing metal-
element bonds of a largely covalent character. Organometallic
chemistry combines aspects of inorganic chemistry and organic
4

chemistry.
5
 Classification of organometallics based on the bond type: -, -, -
b d
bond:

 In evaluations of bond polarity, the electronegativity difference

b t
between th neighboring
the i hb i atoms
t i usually
is ll employed.
l d
 By way of generalization, it may be stated that the chemistry of
main-group
main group organometallics is governed by the group the metal
belongs to, whereas for organotransition-metal compounds, the
nature of the ligand dominates. 主族金属有机化合物的化学主要取定
6
于金属本身的性质 而有机过渡金属化合物的性质则主要受其配体支
于金属本身的性质，而有机过渡金属化合物的性质则主要受其配体支
配。
7
5-2 BASIC CONCEPTS
I. 18-Electron Rule
 The 18e rule: characterizing g and ppredicting
g the stability
y of metal
complexes.
Valence shells of a MT can accommodate 18 electrons: 2 in each of
the five d orbitals (10 in total); 2 in each of the three p orbitals (6 in
total); and 2 in the s orbital.
Combination of these atomic orbitals with ligand orbitals: 9 MOs
which are either metal-ligand bonding or non-bonding. (There are
also some higher energy anti-bonding orbitals). The complete filling
of these nine lowest energygy orbitals with electrons,, whether those
electrons originate from the metal or from any ligand, is the basis of
the 18-electron rule.
 Thermodynamically stable transition-metal organometallics: the
sum of the metal d electrons plus the electrons of conventionally
g
regarded as being
g supplied
pp by
y the ligands
g equals
q 18. 8

W.B. Jensen. J. Chem. Educ. 2005, 82, 28

T bl 1
Table 1. El
Electrons
t d
donated
t dbby common ffragments
t
Neutral Positive Negative Ligands
1 0 2 H; X (F, Cl, Br, I); alkyl
2   CH2=CH2, CO, phosphane, etc.
3 2 4 -ally, cyclopropenyl, NO
4   diolefin
4 6 Cyclobutdiene
5  6 cyclopentadienyl
6   Arene, triolefin
7 6  Tropylium (C7H7+)
8  10 cyclooctatetraene 9
Examples:
p
 TiCl4 3s23p63d24s2
Neutral counting: Ti 4e, Cl 1e; 4+4(1) = 8 valence electrons
Ionic counting: Ti4+ 0e, Cl 2e; 0+4(2) = 8 valence electrons
Conclusion: Having only 8e (vs. 18 possible), we can anticipate that
TiCl4 will be a good Lewis acid. Indeed, it reacts (in some cases
violently) with water, alcohols, ethers, amines.
• Fe(CO)5 3s23p63d64s2
Neutral counting: Fe 8e, CO 2e, 8 + 2(5) = 18 valence electrons
Conclusion: This is a special case, all fragments being neutral.
Since this is an 18-electron
18 electron complex,
complex Fe(CO)5 is a stable compound.
compound

• Fe(C5H5)2 , FeCp2
N t l counting:
Neutral ti F
Fe 88e, C5H5 5e:
5 8 + 2(5) = 18 electrons
l t
Ionic counting: Fe2+ 6e, C5H5 6e: 6 + 2(6) = 18 electrons
Conclusion: Ferrocene is expected to be a stable compound.
compound 10
 [CpFe(CO)2]2
Neutral counting:
C 5 + Fe 8 + 2 CO 4 + Fe-Fe 1 = 18
Cp
Counting electrons for just one iron center
can be done by considering the other iron
as contributing 1 electron to the count.
 CpFe(CH3)(CO)2
Neutral counting:
Cp 5 + Fe 8 + CH3 1 + 2 CO 4 = 18
 Fe2(CO)9
Neutral counting:
3 CO 6 + 3 -CO 3 + Fe 8 + Fe-Fe 1 = 18

tri μ-carbonyl bis(tricarbonyliron)(Fe Fe) 11

tri-μ-carbonyl-bis(tricarbonyliron)(Fe-Fe)
NOTE:
i. These examples show the methods of electron counting, they are a
formalism,, and don't have anything
y g to do with real life chemical
transformations. Most of the 'fragments' mentioned above do not
exist as such; they cannot be kept in a bottle. these formalisms
are only used to predict stabilities or properties of compounds!
ii. The 18-electron rule is just that - a rule, not a law. Many MT
complexes
l d nott follow
do f ll thi rule,
this l and,
d furthermore,
f th compounds
d
which have fewer than 18 valence electrons tend to show
enhanced reactivity.
reactivity In fact,
fact 18 electrons is often a recipe for
non-reactivity in either a stoichiometric or catalytic sense.
iii. It is especially useful for organometallic complexes of the Cr, Mn,
Fe, and Co triads, and applies to compounds such as ferrocene,
iron pentacarbonyl, chromium carbonyl and nickel carbonyl.
12
Violations to the 18-electron rule:
i. Bulky ligands.
 Ti(neopentyl)4 (8 VE)
 Cp*
C *2Ti(C2H4) (16 VE)
 Cp*Cr(CO)3 (17 VE)
 Co(norbornyl)
( y )4 ((11 VE))
C *
Cp* N
Norbornane
b
ii. High spin complexes
降莰烷
 CrCl3(THF)3 (15 VE) 3s23p63d54s1
 [Mn(H
[M (H2O)6]2+ (17 VE)
 [Cu(H2O)6]2+ (21 VE)
iii. Higher electron counts
 Cobaltocene (19 VE)
 Nicklocene (20 VE)
iv. 'Inaccessible' high energy orbitals
 CuCl(CO) (14 VE)
 Vaska
Vaska'ss compound: [IrCl(CO)(PPh3)2] (16 VE) 13
II -Backbonding
II.  Backbonding
-Backbonding (-backdonation):
electrons move from an atomic
orbital on one atom to a *
anti-bonding orbital on another
atom or ligand, in the process
relieving the metal of excess
negative
ti charge.
h
Examples:
Ni(CO)4, Zeise
Zeise’s
s salt

FIG.1. Top: the HOMO and LUMO of CO.

Middle: a sigma bonding orbital in which
CO donates electrons to a metals center from its HOMO.
14
Bottom: the metal center donates electron through a d orbital to CO's
LUMO.
FIG.2. Orbital overlap scheme for the formation of a -type
i
interaction
i b
between an olefin
l fi andd a transition
ii metal:
l (a)
( ) overlap
l off
one lobe of a dx2-y2 orbital from the metal and a -bonding orbital of
the olefin; (b) use of the -antibonding orbital of the olefin.
15
III Hapticity 哈普托数
III.
The term hapticity is used to describe how a group of contiguous
atoms of a ligand are coordinated to a central atom.
atom Hapticity of
a ligand is indicated by the Greek character 'eta', η.
ηn: n = the number of contiguous atoms of the ligand that are bound
t the
to th metal.
t l
 The term is usually employed to describe
ligands containing extended 
-systems
systems or
where agostic bonding is not obvious from
the formula.
 Ferrocene: bis(η
F bi ( 5-cyclopentadienyl)iron
l t di l)i
 Zeise’s salt: K[PtCl3(η2-C2H4)].H2O
 Uranocene:
bis(η8-1,3,5,7-cyclooctatetraene)uranium
 W(CO)3(PPri3)2(η2-H2)
 IrCl(CO)[P(C6H5)3]2(η2-O O2) 16
TABLE 2. Electrons donated by "-ligands" vs. hapticity

Ligand Electrons contributed Electrons contributed

(neutral counting) (ionic counting)
η1-Allyl 1 2
η3-Allyl, cyclopropeny 3 4
η3-Allenyl 3 4
η2-Butadiene 2 2
η4-Butadiene 4 4
η1-cyclopentadienyl 1 2
η5-cyclopentadienyl
cyclopentadienyl 5 6
cyclohexadienyl
η2-Benzene 2 2
η6-Benzene 6 6
η7-Cycloheptatrienyl 7 6
η8-Cyclooctatetraenyl
C l t t t l 8 10 17
 Changes in hapticity
The hapticity of a ligand can change in the course of a reaction.

The η5-cyclopentadienyl changes to an η3-cyclopentadienyl, giving

g ligand
room on the metal for an extra 2-electron donating g 'L‘. 18
 Hapticity vs.
vs denticity
Polydentate ligands coordinate via multiple coordination sites within
the ligand. Denticity refers to the number of atoms in a single ligand
th t bind
that bi d to
t a central
t l atom
t i a coordination
in di ti complex.
l
Examples:
 1,2-bis(diphenylphosphino)ethane,
1 2 bis(diphenylphosphino)ethane (Ph2PCH2CH2PPh2)
dichloro[ethane-1,2-diylbis(diphenylphosphane)-2 P]nickel(II)
 titanocene dichloride: (Cp2TiCl2)
dicholorobis(η5-2,4-cyclopentadien-1-yl)titanium

19

Metal-EDTA chelate
5 3 IMPORTANT TYPES OF REACTIONS
5-3
I. Oxidative addition/Reductive elimination
 In oxidative addition, a metal complex with vacant coordination
sites and a relatively low oxidation state is oxidized by the insertion of
the metal into a covalent bond (X－Y).
(X Y)
 Both the formal oxidation state of the metal and the electron count
of the complex
p increase byy two.
 Oxidative additions can occur with the insertion of a metal into
many different covalent bonds, they are most commonly seen with
HH and Csp3halogen bonds.
Cl H
H H H
Vaska’s Ph3P Ir PPh3 Ph3P Ir PPh3
complex: OC OC
Cl
Ir(I) Ir(III) IR: CO cm-
VE 16 18 1
CN 4 6 Vaska's complex: 20
1967
Vaska's + I2: 2067
A reductive elimination involves the elimination or expulsion of a
molecule from a transition metal complex. In the process of this
elimination, the metal center is reduced by two electrons.

 The groups being

eliminated must be in a
mutually cis orientation.
 A series of reactions
involving an oxidative
addition, a rearrangement
and then a reductive
elimination form the basis
for a variety of industrially
21
important catalytic cycles.
II. Transmetalation
 Transmetalation is a general chemical reaction type describing the
exchange of ligands between two metal centers. The metal centers
need not be the same. The ligands R and R' can be organic or
inorganic.

 Transmetalation is important in the synthesis of various

organometallic compounds. This reaction type also appears frequently
in the catalytic cycle of various metal catalyzed organic reactions.
PdLn
Negishi coupling: R X + R' Zn X' R R'

R R' R X
Pd(0)
Reductive Oxidative
Eli i ti
Elimination addition

R PdII R' R PdII X

22

X Zn X' transmetalation R' Zn X'

III. Carbometalation
 Carbometalation is an reaction involving the nucleophilic addition
to alkenes and alkynes of a diverse range of organometallic reagents
such as organolithium compounds,
compounds organocopper compounds and
Grignard reagents according to the following general alkyne scheme:

tamoxifen

23
IV. Migratory insertion
A migratory insertion reaction is when a cisoidal anionic and neutral
ligand on a metal complex couple together to generate a new
coordinated anionic ligand.
ligand This new anionic ligand is composed of
the original neutral and anionic ligands now bonded to one another.

Anionic: H-, R- (alkyl),

Ar-(aryl), acyl-, O2- (oxo)
Neutral: CO, alkenes,
alkynes, carbenes

 No change in formal oxidation state (exception: alkylidenes).

 The two groups that react must be cisoidal to one another.
 A vacant coordination site is generated by the migratory insertion.
 Migratory
Mi t insertions
i ti are ffavored
d on more electron-deficient
l t d fi i t metal
t l 24
centers.
 Alkene Migratory Insertions.
Alkene and hydride/alkyl migratory insertion is the basis for almost all
transition metal
metal-based
based polymerization catalysts.
catalysts

Coordination Migratory
insertion

A polymerization
l i ti i just
is j t many, many migratory
i t i
insertions
ti off an
alkene and alkyl (the growing polymer chain) interspaced with
alkene ligand addition reactions.
25
 An alkene and a hydride usually react via a migration of the
hydride to the coordinated alkene ligand:

The backwards reaction, of course, is a β-hydride elimination and is

usuallyy q
quite favorable if there is an empty
p y orbital cis to the alkyl
y
ligand. Thus, the general importance of having a trapping ligand to
coordinate to the empty orbital generated from the migratory
26
insertion.
V. 
-Hydride
y elimination
Elimination reactions are just the reverse of migratory insertion
reactions.
 -Hydride
 Hydride elimination is a reaction in which an alkyl group bonded
to a metal centre is converted into the corresponding metal-bonded
hydride and an alkene.

The key points to remember are:

i. No change in formal oxidation state (exception: alkylidenes).
ii. A vacant orbital is cisoidal to the group to do an elimination
reaction on. Alternatively, a cisoidal labile ligand that can easily
dissociate to open up an empty orbital.
27
 Avoiding
g β-hydride
β y elimination:
i. to employ an alkyl ligand that lacks a β-hydrogen (methyl or neopentyl).
ii. It is also inhibited when the reaction would produce a strained alkene.

iii. The beta position may be blocked by non-hydrogen atoms.

iv. If the metal center does not have empty coordination sites, for
example, by the complex already having 18 electron configuration, β-
hydride elimination is not possible as well.
28
5-4
5 4 MAIN-GROUP
MAIN GROUP ORGANOMETALLICS
I. PREPARATION
 Direct Synthesis

Li + C4H4Br C4H9Li + LiBr

Mg + C6H5Br C6H5MgBr

Mixed metal synthesis:

Hf(NaX) boosts the driving force.

Side reactions:

29
 Transmetallation

H = -35 kJ/mol
This general method may be applied to M = Li ~ Cs, Be ~ Ba, Al, Ga,
S Pb,
Sn, Pb Bi,
Bi Se,
S Te,
T Zn,
Z Cd.
Cd
 Metal exchange
4 PhLi + (CH2=CH)4Sn 4 (CH2=CH)Li + Ph4Sn

This
s method
et od iss use
useful
u for
o making
a g ce certain
ta o organolithium
ga o t u co compounds
pou ds
from derivatives of less electropositive metals.
 Metal Halogen Exchange
n-BuLi + PhX n-BuX + PhLi
y n-BuH < PhH
Acidity: 30
 Metallation of CH acids
Metallation (replacement of H by M) are acid/base equilibrium. The
arenes with their higher acidities are appropriate substrates and the
method is particularly valuable for the preparation of aryllithium
compounds.
R R
H Li
+ BuLi + BuH

R = MeO, Me2N, CONMe2, SO2Me, etc.

PhNa + PhCH3 PhH + PhCH2Na

31
 Carbometallation and Hydrometallation

2
+

cis

2 5 2 2 2 2 5 2 2 3

32
II. Organolithium reagents
 Organolithium reagents can be aggregated, with lithium
coordinating
g to more than one carbon atom and carbon
coordinating to more than one lithium atom.

Li d (Li C) = 2.31Å
2 31Å
d (Li Li) = 2.56Å
CH3
d (C C) = 3.68
Li C Li 68

Schematic drawing of the unit (LiCH3)4

Solid methyllithium: cubic body-centered packing

of (LiCH3)4 units, the latter consisting of Li4-
tetrahedron with methyl groups capping the
triangular faces. 立方体心堆积
 In the aggregates (LiR)n, the “electron n-Butyllithium
deficiency” is compensated for by the formation of
deficiency 33

multicenter bonds.
 Three general factors affect aggregation: the electrostatic
interaction between opposite charges, the coordination sphere of
lithium (solvent molecules or Lewis base) and the steric hindrance
of the hydrocarbon part.
part

LiR Solvent Aggregation

LiCH3 hydrocarbon Hexamer (Li
( 6 octahedron))
THF, Et2O Tetramer (Li4 tetrahedron)
Me2NCH2CH2NMe2 monomer
n-BuLi cyclohexane hexamer
Et2O tetramer
t-BuLi hydrocarbon tetramer
PhLi THF, Et2O dimer
PhCH2Li THF, Et2O monomer
C3H5Li (allyl) THF monomer
34
 REACTIONS
 Metalation or Li/H exchange reaction: The metalation reaction is
an important synthetic method for the preparation of many
organolithium compounds.
compounds

O O O
S Li (EtO)2P Li R Li Li
Ph S
Li

• R
Reaction
ti with
ith ketones
k t andd aldehydes
ld h d to t alcohols.
l h l
• Reaction with carboxylic acid salts and acid chlorides to the
corresponding
p g ketone.
• Reaction with oximes to the corresponding amines. (肟)
• Reaction with isonitriles to the corresponding lithium aldimine (醛
亚 胺 ). ) Subsequent
S b t hydrolysis
h d l i effectively
ff ti l converts
t th
the
organolithium compound to its aldehyde.
• Reaction with certain epoxides
p to the corresponding
p g alkenes. 35
 O O
LiH CH3Li
OH O Li
DME, Heat Et2O

CH3 O
C(OLi)2 aq. HCl
CH3

N
Li
O Li
C10H21 C10H21
o
THF/pentane, 0 C to r.t.
36

Organic Syntheses, Vol. 85, p1 (2008)

III. Organomagnesium and Organozinc
 In many ways the chemistry of group 2 elements (the alkaline earth
metals) mimics that of group 12 elements because both groups have
filled s shells for valence electrons.
Group 2 Ba Electropositive character of the
Sr metal
Ca
Mg and
Be
reactivity of organometallics in
Group 12 Zn heterolytic reactions
Cd
Hg decreases

Among the organometallic compounds of groups 2 and 12,

organomagnesium
i compounds
d are off prime
i i
importance b
because off
their application in organic synthesis. Organomagnesium
compounds combine in a unique way high reactivity and ease
37
access.
Grignard reagent
 Grignard reagents are formed via the action of an alkyl or aryl
halide on magnesium metal. Typical solvents are Et2O and THF. The
reaction proceeds through single electron transfer..

 The addition of I2 activates the Mg surface; MgI2 thus formed,

binds the last traces of water in the reaction mixture.
 Schlenk equilibrium,
equilibrium Grignard reagents form varying amounts of
diorganomagnesium compounds (R = organic group, X = halide):

38
39
40
 Also the Grignard reagent is very useful for forming carbon-
heteroatom bonds.

41
ORGANOZINC COMPOUND
Several general methods:
 Oxidative addition. The original Et2Zn synthesis by Frankland was
an oxidative addition of C5H2I to Zn metal with hydrogen gas as a
"protective" blanket.
 Halogen zinc exchange. Two main halogen zinc exchange
reactions are iodine zinc exchange and boron zinc exchange.
exchange
 Transmetalation. In a typical transmetalation, diphenylmercury
reacts with zinc metal to Ph2Zn and metallic Hg in Et2O.

42
43
IV. ORGANOMETALLICS OF THE BORON GROUP
A. Organoboron Compounds
g
Organoborane or organoboron
g compounds
p are organic
g derivatives of
BH3, for example trialkyl boranes. Organoboron compounds are
important reagents in organic chemistry enabling many chemical
transformations, the most important one called hydroboration.

 Characteristics:
• CB
C B bond,
b d lowl polarity
l it (electronegativity
( l t ti it C 2.55,
2 55 B 2.04)
2 04)
• Electron-rich groups like vinyl or phenyl provide the CB bond
with partial double bond character.

44
 Organoboron
O b h d id
hydrides R2BH and
d RBH2 form
f di
dimers which
hi h always
l
display hydride bridges rather than alkyl bridges:

bridging

H H Hb
H R H R Ht R
122 97° B B B B
H H H H R b Ht
1.32Å 1.19Å R R H
(R2BH)2 (RBH2)2 terminal

Stretching frequency Intensity

Hb
B B symm. 1500-1600 cm-1 strong
Hb
B B asymm. 1850 medium
di

2500-2600
B Ht
45
 Hydroboration-oxidation
Hydroboration oxidation reaction. One of the most versatile
methods in organic synthesis is hydroboration. Herein, rather than the
resulting organoboranes themselves, the products of their subsequent
p
reactions are important:

 Regioselective  anti-Markovnikov addition, the hydrogen adds

to the most-substituted
most substituted carbon.
carbon The reason is that boron is less
electronegative than hydrogen.
 Stereospecificity  addition in a syn mode, that is on the same
f
face off the
th alkene.
lk 46
47
 The
Th so called
ll d anti-Markovnikov
ti M k ik addition
dditi is
i mostt pronouncedd when
h
the boron compound has very bulky substituents. Thus, bis-(1,2-
dimethylpropyl)borane ((“disiamylborane”)
disiamylborane ) adds to 11-pentene,
pentene, leaving
2-pentene, unaffected (selectivity > 99%).

48
B Organoaluminum Compounds
B.

The chemistry of organoaluminium compounds can be understood in

t
terms off the
th dynamic
d i nature
t off the
th C−Al
C Al bond
b d and
d the
th high
hi h Lewis
L i
acidity of the monomeric species.

1H NMR: At −25C the 1H

NMR of Me6Al2 comprises
two signals in 1:2 ratio, as
expected from the solid
state structure.
structure At 20 20C
C,
only one signal is observed
Al2Me6 exists as a dimer. the because exchange of
metalloids are connected by a 3- terminal and bridging
center-2-electron bond as with methyls is too fast to be
diborane
diborane. resolved
l d by
b NMR.
NMR

49
 Laboratory preparation

 Metathesis with RLi or RMgX

AlCl3 + 3 BuLi → Bu3Al + 3 LiCl
 Transmetalation
2 Al + 3 HgPh2 → 2 AlPh3 + 3 Hg
 Industrially, simple aluminium alkyls (Me, Et) can be prepared by a
direct process:
4 Al + 6MeCl  2 Me3Al2Cl3  Me4Al2Cl2 + Me2Al2Cl4  Me4Al2Cl (l)
+2N Na[MeAlCl ( )  Me
[M AlCl3] (s) M 3Al + Al + 6 NaCl
N Cl
 Diisobutylaluminium hydride is
Prepared by -hydride
 hydride elimination:
(i-Bu3Al)2  (i-Bu2AlH)2 + 2(CH3)2C=CH2
DIBAl H
DIBAl-H 50
 Reactions
 Organoaluminium compounds are hard Lewis acids and readily
form adducts with bases such as pyridine, THF and amines.
 Reaction
R ti with
ith protonic
t i reagents:
t
AlR'3 + ROH  (R'2Al−OR)n + R'H
 Hydroalumination of C=C
C C double bonds

 Readiness: RCH
RCH=CHR CHR < R2C C=CH
CH2 < RCH
RCH=CH CH2 < CH2=CH
CH2
 Stereosepecity (cis) and regioselectivity (anti-Markvonikov).

51
52
V ORGANOSILICON
V.
Organosilicon compounds are organic compounds containing carbon
silicon bonds.
bonds
 Like carbon, the organically bound silicon is tetravalent and
tetrahedral.
CSi 1.86 Å, 318 kJ/mol; electronegativity: Si 1.90, C 2.55
 Preparation

T
2 2

4 4
3 3
2 2 4 2 2 3

3 2 2 2 3 53
 Property and Reactions

 The trimethylsilyl cation, Me3Si+, departs from a carbon atom

more readily than does a proton.
 Beta-silicon effect: The beta-silicon effect also called silicon
h
hyperconjugation
j ti i a special
is i l type
t off hyperconjugation
h j ti andd
describes the stabilizing effect of a silicon atom placed in a position
once removed (β) from a carbocation.

54
These two properties are manifest in reactions of vinylsilanes.
vinylsilanes Thus,
Thus
many electrophiles give substitution rather addition, the silicon being
eliminated as a cation and the configuration at the double bond is
retained.
t i d

55
 H2O

R3Si R3Si H
+
H HX
slow
+ R3SiOH2+

HX = CF3CO2H, RfSO3H

Cl Cl Me3Si SiMe3 I I
Me3SiCl/Mg ICl
HMPT CCl4
Cl Cl Me3Si SiMe3 I I
I

SiMe3 ICl
+ Me3SiCl

COR

RCOCl 56
+ Me3SiCl
AlCl3
 Th
The readiness
di t undergo
to d h t l ti Si-C
heterolytic Si C bond
b d cleavage
l
(desilyation):

The desilyation proceeds much

more rapidly if good leaving
groups are present (-effect)
( effect).
Alsol:
(PhCH2O)2MeSiCH2CH2Cl 57
5 5 ORGANOMETALLICS OF THE TRANSITION
5-5
ELEMENTS
The full variety of organometallic chemistry presents itself in the realm
of transition metals. Contributing factors include:

 For transition metals,, the ((n-1)d,

) , ns and np
p orbitals must all be
regarded as regular valence orbitals.

 Partial occupation of these orbitals gives transition metals both

electron-donor and electron-acceptor properties (-donor/-acceptor
synergism).

 Various forms of metal-metal multiple bonding with or without

additional bridging ligands.
ligands

 The ability to change the coordination number together with the

lability off metal-carbon -bonds offers
ff possibilities for 58
f organometallic
catalysis.
I. ALKENE COMPLEXES
 Bonding and Structure: Dewar-Chatt-Duncanson model.

i. A synergistic bonding situation:

the greater the -donation to the
metal, the greater the  -
backbonding.
ii. The greater the electron density
b kd
back-donated
t d into th ** orbital
i t the bit l on
the alkene, the greater the
reduction in the C=C bond order.
iii. Electronic factors: CF2=CF2 will
bind more tightly than ethylene to
a low
o valent
a e t metal
eta co
complex.
pe
iv. Steric factors: The stability of
substituted alkene complexes is
l
less th that
than th t off ethylene-complex.
th l l59
 O
C

H H R
CO
C H C Fe
Cl CO
Pt C C
1 37A
1.37A H
Cl Cl H H C
H O
K[PtCl3(C2H4)] H2O
CH2=CHCNFe(CO)4
(Zeise's salt) C2H4Fe(CO)
( )4
free C=C 1.34A

CO
CR2
Coordinatively unsaturated Ph3P
complexes can add olefinic IrCl(CO)(PPh3)2 + R2C CR2 Ir
ligands without replacement Ph3P CR2
of another group. Cl
16 VE 18 VE

 Reaction. The bonding of an alkene to a transition metal can

activate the ligand to electrophilic or nucleophilic attack depending on
the nature and chargeg of the metal center. 60
II ALLYL COMPLEXES
II.
 Bonding and Structure. Allyl ligands are ambidentate ligands that
can bind in both a monohapto and trihapto form.
form

1H NMR: Hanti 1 ~ 3 ppm,

Hsyn 2~5 ppm, Hmeso 4 ~
CC: 1.35 ~1.40Å
6.5 ppm.
CCC : 120 13C NMR: terminal 80 ~
90 ppm, central 110~130
ppm
Hmeso and
d Hsyn are bent
b t towards
t d the
th metal
t l (7 andd 13 degrees
d f
from planar)
l )
while Hanti is bent 31 degrees away. In 3-allyl-NiCl, the Ni-C1 and Ni-C3
distances are approximately 2.03 Å and Ni-C2 is 1.98 Å.
61
 H 12°
H C
C H
H
C
H C
C H3C
Pd Cl Ni
C
C Pd
Cl C
C H
H H C
C C CH3
H
12°
H
both C-C distances: 1.38 Å C-C distance: 1.41°
C-C--C angle: 120 ° C-C-C angle: 119°
Pd-C distances: 2.11Å Cc-Ni: 1.98 Å
C-C-C plane with Pd2Cl2 plane: 111° Ct -Ni: 2.02 Å
3
-Allylpalladium Chloride Dimer Bis(methylallyl)nickel

 In the 1H NMR spectra of allyl complexes, syn- and anti-protons of

62
the terminal CH2 groups are generally nonequivalent.
 Synthesis: Most syntheses of trihapto allyl complexes involve the synthesis of
a monohapto complex which then displaces a ligand to give the trihapto form.

63
 R
Reactions:
ti

With nucleophiles, stereoselective

Insertion reactions

Reductive elimination
64
III. CARBONYL COMPLEXES
 Carbonyl complexes are
compounds that contain
carbon monoxide as a
coordinated ligand.
 This bondingg are
synergistic. The more
sigma donation by the
carbonyl (or other sigma-
donors on the metal
center) the stronger the -
center), 
backbonding interaction.

Free C O
d CO = 1.128 A
v CO = 2143 cm-1 65
Ni(CO)4 v CO 2057 cm-1
CO(CO)4- v CO 1886 cm-1
IV METALLOCENE
IV.

 A metallocene is a compound with the general

formula (C5H5)2M consisting of two
cyclopentadienyl anions (Cp, which is C5H5-)
bo nd to a metal center (M) in the oxidation
bound o idation state
II. Bis(cyclopentadienyl) complexes are sometimes
called "sandwich
sandwich compounds
compounds”.. Some metallocene
derivatives, such as Cp2TiCl2, have their Cp rings
tilted with respect to each other and are called
"bent metallocenes", while complexes with only
one Cp ligand have been colorfully described as
having "half sandwich" and "3-legged
"3 legged piano stool"
geometries, e.g., methylcyclopentadienyl
manganese
g tricarbonyl.
y 66
 Bonding of Cp-ligands:
Cp ligands: Cp-ligands
Cp ligands are generally bound via all 5
carbon atoms to a metal centre (η5-coordination, π-complexes). In
rare cases, the Cp unit can bond through three carbon atoms, like in
[( 3-Cp)WCp(CO)
[(η C )WC (CO)2]; ] or through
th h one carbon
b atom,
t as in
i [(η
[( 1-
Cp)FeCp(CO)2].

67
 Bonding of Cp-ligands: Cp-ligands are generally bound via all 5
carbon atoms to a metal centre (η5-coordination,, π-complexes).
p ) In
rare cases, the Cp unit can bond through three carbon atoms, like
in [(η3-Cp)WCp(CO)2]; or through one carbon atom, as in [(η1-
Cp)FeCp(CO)2].
 Spectroscopic features
1H NMR: Cp rings appear as singles in the range of 4.0 to 5.5 ppm.
Cp* ligand typically appear at 1-2
1 2 ppm
13C NMR: the carbons of CP are also equivalent, 80-95 ppm; Cp* 20-

30 ppm.
 Synthesis of Cp Complexes

68
 Property and Reactions:
C5H5FeC5H4NH2: a stronger base than aniline
C5H5FeC5H4COOH: a weaker acid than benzoic acid
The ferrocenyl group therefore acts as an electron donor.

+ +
6

3 3
3
3

3
69
V DIHYDROGEN COMPLEXES
V.
 Dihydrogen complexes are transition metal species in which a
molecule of molecular hydrogen acts as a two electron sigma donor
to the metal center.

70
VI TRANSITION METAL CARBENE COMPLEX
VI.
 A transition metal carbene complex is an organometallic compound
featuring a divalent organic ligand.
ligand The divalent organic ligand
coordinated to the metal center is called a carbene.
 Described often as M=CR2, they represent a class of organic ligands
intermediate between alkyls (-CR3) and carbynes (≡CR).

71
Metathesis polymerization

[Cat.]
* *
n
[cat.] = Mo(=CHBut(NAr)(OR)2

C Mt + C Mt CH Mt CH Mt
H H

*
*
n
Pr Pr
N
(CF3)2MeCO Ph
* Mo
* (CF3)2MeCO Me
Me

n 72
5 6 ORGANOMETALLIC CATALYSIS
5-6
pro memorial: A catalyst accelerates the rate of a thermodynamiclly
f
feasible
ibl reaction
ti b opening
by i a lower
l activation
ti ti energy pathway.
th If
alternative routes exist, a catalyst can enhance product selectivity by
accelerating just one of the competing reaction sequences.
I. Mode of Action of Transition-Metal Complexes in Catalysis
 The coordination of the reaction partners to a transition metal brings
t h e m i n t o c l o s e p r o x i m i t y, t h u s p r o m o t i n g t h e r e a c t i o n .
 Through coordination to a transition metal, a reaction partner can
become activated for subsequent reactions.
reactions
 The coordination of an organic substrate to a transition metal can
facilitate nucleophilic attack.
Catalytically active systems therefore must possess vacant coordination
sites or be able to generate them in a primary dissociation step.
73
 Heterogeneous Catalysis
The vacant coordination site is located at a phase boundary
(solid/liquid, solid/gas), i.e., only the surface atoms are catalytically
active.
ti
Advantage: the easy recovery of the catalyst;
Disadvantage:g low specificity,
p y, relatively
y high
g reaction temperatures
p
and difficulties in the mechanistic study.
 Homogeneous Catalysis
The catalyst can be tailor-made by ligand variation and is obtained
reproducibly. high specificity, the catalysis can often be carried out at
low temperatures.
temperatures Ideally,
Ideally the catalyst complex is stable in more than
one coordination number and, through fine-tuning of chemical bond
strength (variation of the ligands), capable of holding a substrate
molecule selectively but not too tightly.
 The most important homogeneous catalysis: the “late transition
metals” complexes Ru,
Ru Co,
Co Rh,
Rh Ni,
Ni Pd and Pt (M d8, d10).
) 74
II. CATALYTIC REACTIONS AND THE 16/18 VE RULE
Elementary organometallic reactions: Characteristic variables
CN VE OS reaction
1/+1 0 0 (1)
1/+1 2/+2 0 (2)
+2/2
2/ 2 +2/2
2/ 2 +2/2
2/ 2 (3)
1/+1 2/+2 0 (4)
0 2/+2
2/ 2 +2/2
2/ 2 (5)

VE: Change in the number of

valence electrons at the central
metal
OS: Change in the oxidation
state of the metal (usual
convention: – hydride, -alkyl, -allyl,
and –pentadienyl are regarded as
75
anions)
CN: Change in the coordination
number
 3 4
14 9 1

3 2

2 4 2 3 4
3
3
3 2
3 2
3
3
0 10 II 8
d complex
l d complex
l
Lewis-base ligand association oxidative addition

76
 The formulation of a possible reaction mechanism for an
organometallic
lli catalysis
l i isi assisted
i db by the
h 16/18
6/ 8 VE rule.
l
Elementary reaction step Expected for  It should be
complexes stressed that the
16/18 VE criterion in
Lewis-acid ligand increasing regarded
dissociation as an undue restraint.
16 18 VE
16,
Lewis-acid ligand  The actual catalyst
association of a reaction is not
always known. The
Lewis-base
Lewis base dissociation catalyst
t l t often
ft refers
f
Reductive elimination 18 VE to the “precatalyst”,
Usually a well-known
Migratory insertion substance like (PPh3)
Oxidative coupling 3RhCl, which
reacts with H2, CO or
Lewis-base association other substrates in
Oxidative addition 16 VE solution
l i to
generate the active
Extrusion catalyst. 77
Reductive decoupling
III. EXAMPLES OF CATALYTIC APPLICATIONS

Wilkinson's catalyst
dissociation of
one or two PPh3

Reductive
R d ti
elimination Oxidative
(extrusion of addition
the alkane)

Intramolecular hydride
transfer (olefin insertion) -complexation of alkene

78
 The Cativa processes

79
 Palladium-catalyzed coupling reactions
In 2010, the Nobel Prize in Chemistry was awarded to Richard F. Heck, Ei-ichi
Negishi and Akira Suzuki for their work on palladium-catalyzed cross
couplings in organic synthesis.

Heck reaction

80
Negishi coupling

81
Suzuki Coupling

82
An example is the Sonogashira reaction:

83