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01 1350977450 79497 PDF
01 1350977450 79497 PDF
Organometallic
Chemistry
Advanced Organic Chemistry
5 1 INTRODUCTION
5-1
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:
• 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
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
HH and Csp3halogen 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.
R R' R X
Pd(0)
Reductive Oxidative
Eli i ti
Elimination addition
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.
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:
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-BuH < PhH
Acidity: 30
Metallation of CH 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
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
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
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
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:
• CB
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 CB 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
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:
48
B Organoaluminum Compounds
B.
49
Laboratory preparation
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.
CSi 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
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):
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
63
R
Reactions:
ti
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.
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)
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