Chimica organometallica

I composti organometallici contengono legami diretti metallo-carbonio.

Possono verificarsi legami o e/o n

Gruppo principale: metalli elettropositivi: spesso idruri/alchili 3c-2e o 4c-2e

CH3 CH, CH,

(AIMe,),
Al Al

(MeLi)4
CH, CH, CH,
Cobalimine

contengono CoCbond
(Vitamina B12)
-) Sale di Zeise sintetizzato nel 1827 = K[P(C,H,)CI,]• H,0 Confermato di
avere H,C=CH, come ligando nel 1868 Struttura non
completamente nota fino al 1975
 M-CO

M-CS

-M
 Chimica dei composti organometallici

Metallo-alchili M------C

Metallo - T-acidi

M----CO, M--- M ---- CN

M----Cp Cp= n;-CgH

I composti organometallici ionici di metalli alcalini o alcalino-terrosi sono noti da tempo:

(CçHs),C Nat
 Decomposizione dei complessi alchilici tramite eliminazione B:

M-C= 150-350 KJ/mol

Stabilità termodinamica - Labilità cinetica

M-CH,-CHR → M-H+ CH,=CR,

Condizioni per l'eliminazione B:

- il carbonio B deve contenere un atomo di H
 Come prevenire l'eliminazione dell'
idrogeno B?
• Nessun idrogeno B
-CH, -CH,CMes, -CH,SiMe, -CH,Ph

Nessun sito vuoto è cis rispetto all'alchile

Et

OH,

Prodotto di eliminazione instabile

I complessi alchilici dei metalli di transizione sono importanti come catalizzatori, ad es. Reazioni di polimerizzazione e
idroformilazione delle olefine:

morbido
 Sintesi di metalli alchili
Metatesi (scambio)

TiCI, + 4 BzMgCI > TiBZ4 + 4 MgCl,

(Bz = benzile, C,H,CH)

wCl, + 6 Al(CH,), → W(CHz)6 + 6 Al(CH̟),ci

Mel
Attacco elettrofilo ai Mn(CO) metallici MeMn(CO)5

Ar Ar

Inserimento
CH4
-Co-H )N-ÇoEt

FN
Ar Ar
 Sintesi di metalli alchili
Addizione ossidativa

spesso inizia con un attacco elettrofilo

Me

-0. L=P(OPn)3
Ro Mel l
OL
Rh L=PPh,
Io
l

+1 +3

Ircl(co)[P(Ph)al, + CH,l > Ir(CH,)CI()(CO)[P(Ph)J,

 Grignard Reagents
Preparation of Grignard Reagents:

Br Mg MgBr
Et2O
Butylmagnesium Bromide
(Grignard Reagent)

Br MgBr
Mg
Et2O

Phenylmagnesium Bromide
(Grignard Reagent)
 Organometallic Reactions

• Can Act as Nucleophiles Towards Polarized Carbonyl Groups

• Very Strong Lewis Bases (React with Acidic Protons)

• Basicity Necessitates Dry Conditions (Avoid Reaction with H2O)

• Reason For Basicity: Carbanion-Like Behavior

• Strong Enough Bases to Deprotonate Terminal Alkynes (pKa??)

• With No Acidic Protons, Can Do Nucleophilic Substitution

 Reactions of Grignards with Epoxides

O 1. Et2O
MgBr OH
+ +
2. H3O

O 1. Et2O
MgBr OH
+
2. H3O+

• Grignard Reagents Nucleophilically Open Epoxides

• Generally Attack Less Substituted Carbon (Steric Hindrance)

• View This as Carbanion Attacking in SN2 Reaction.

 Reactions of Grignards with Carbonyls
➢ Formaldehyde → 1° Alcohols

➢ Higher Aldeydes → 2° Alcohols

➢ Ketones → 3° Alcohols

➢ Ester → 3° Alcohols

• Attack of Grignard Generates Alkoxide; Protonate (HCl) to get OH

MgBr
O
Et2O OH
+
H H
Me

MgBr
O
Et2O OH
+
H3 C H
Me
Me
MgBr
O
Et2O OH
+
H3 C CH3
 Reactions of Grignards with Esters
Me OH

MgBr
O
Et2O
+
H3C OCH3

• Grignard Reagents React Twice with Esters → 3° Alcohols

• Grignard Reactions Quite Useful in Wide Range of Alcohol

Syntheses (with Varying Degrees of Substitution)
 Organolithium Reagents
Common Solvents for Organolithium Reagents:

O
O
Diethyl Ether Tetrahydrofuran

Preparation of Organolithium Reagents:

Br 2Li, -10 oC Li
+ LiBr
Et2O
Butyllithium
(Alkyl Lithium Reagent)

• Halide Reactivity: RI > RBr > RCl (F Not Often Used)

• RLi Reactive, Carbanion-Like Species (React Slowly with Ethers)

 Reactivity of the M-C bond
Polar  reactive towards e.g.
• Water: M-OH + H-C

Me3Al explodes with water; Me4Sn does not react.

• Oxygen: M-O-O-C

Me2Zn inflames in air; Me4Ge does not react.

• Carbonyl groups: M-O-C C

MeLi adds at -80°C, Me3Sb not even at +50°C.

Oxidation and hydrolysis: large driving force

Bond strengths in kcal/mol:
Al-C 65 As-C 55 Si-C 74
Al-O 119 As-O 72 Si-O 108
Al-Cl 100 Si-Cl 91
17
Organometallic compound that acts as a Nucleophile

❖ Addition to polar C=X bonds

(C=O, C=N,)

R
+
R M
O OM
❖ Substitution at sp2 carbon
(often via addition)

OR' R OR' R
+ - MOR'
R M
O OM O
As a base
❖ More prominent in polar solvents: as a free R- acting as base

❖ Elimination

R M + RH + MX
X

❖ Metallation
H M
R M + RH
Me2N Me2N

chelate effect more important than inductive effect!

Alkene ligands

Dewar-Chatt-Duncanson model

The greater the electron density back-

donated into the * orbital on the
alkene, the greater the reduction in the
C=C bond order
Alkyne ligands:

Similar to alkenes
alkynes tend to be more
electropositive. They bind
more tightly to a transition
metal than alkenes. Alkynes
will often displace alkenes

Difference is 2 or 4 electron
donor
sigma-type fashion (A) as we
did for alkenes, including a -
backbond (B)

The orthogonal set can also

bind in a  -type fashion
using an orthogonal metal d-
orbital (C)
Legami multipli
Metallo-Carbonio
 Syntheses of metal carbonyls

For Ni and Fe, the homoleptic or binary metal carbonyls can be made by the direct
interaction with the metal.

In other cases, a reduction of a metal precursor in the presence of CO (or using CO as

the reductant) is used.

Carbon monoxide also reacts with various metal complexes, most typically filling a
vacant coordination site or performing a ligand substitution reactions.

Occasionally, CO ligands are derived from the reaction of a coordinated ligand

through a deinsertion reaction
 Metallo - Carbonili
I carbonili omonucleari obbediscono alla regola
dei 18 elettroni tranne V(CO)6 che ne possiede 17
ed é stabile.
Esso possiede simmetria ottaedrica con
configurazione d5 → 2T2g leggermente distorta per
effetto Jahn-Teller.
Il momento magnetico  é tipico di un elettrone
spaiato. A 6.6 K si ha una transizione di fase:
Paramagnetico → antiferromagnetico.
A 4.2 K non si osserva più paramagnetismo.
Cr(CO)6; Mo(CO)6, W(CO)6
Stabili e non esistono gli analoghi dinucleari

Fe(CO)5; Ru(CO)5, Os(CO)5

Instabili e difficli da preparare.

Ni(CO)4
Stabile

Pd(CO)4; Pt3(CO)4
In matrici di gas nobili a 20K.

Mn(CO)5 a 17 e Mn2(CO)10 a 18 e Mn-Mn

Tc(CO)5 a 17 e Tc2(CO)10 a 18 e
Re(CO)5 a 17 e Re2(CO)10 a 18 e
ReMn(CO)10 a 18 e
Co(CO)4 a 17 e Co2(CO)8 a 18 e
Radicali
Synthesis of carbonyl complexes

Direct reaction of the metal

– Not practical for all metals due to need for harsh

conditions (high P and T)

– Ni + 4CO →Ni(CO)4
– Fe + 5CO →Fe(CO)5
Reductive carbonylation
– Useful when very aggressive conditions would be
required for direct reaction of metal and CO

» Wide variety of reducing agents can be used

– CrCl3+ Al + 6CO → AlCl3 + Cr(CO)6
– 3Ru(acac)3 + H2 + 12CO → Ru3(CO)12 +
N.B. From the carbonyl complex we can synthesize other derivatives
 Wilkinson’s Catalyst (NOBEL : 2001)
Chlorotris(triphenylphosphine)rhodium(I) for the Hydrogenation of
Unsaturated Hydrocarbons.

Ph3P PPh3

Rh

Cl PPh3
square planar d8 configuration

H H
-CH=CH- + H2 → -CH-CH-
 WC in alkene Hydrogenation: Catalytic Steps
(1) Oxidative addition

H
Ph3P PPh3 Ph3P PPh3
Rh + H2 Rh
Ph3P Cl Ph3P H
Rh+1 Cl
Rh3+
(2) Ligand Dissociation

H H
Ph3P PPh3 Ph3P
Rh Rh H + PPh3
Ph3P H Ph3P
Cl Cl
 WC in alkene Hydrogenation: Catalytic Steps
(3) Ligand Association

H H CH
Ph3P H H2
Ph3P CH2 Ph3P Rh
Rh H + Rh CH2
PPh3
Ph3P CH2 Ph3P Cl H
Cl
H2CCl CH2
(4) Migration/Insertion

H H CH2
Ph3P H CH
H 2
Ph3P Rh CH2
Cl Rh
CH2
PPh Ph3P
3
Ph3P H Rh H
H2CCl CH2 Ph3P
Cl
 WC in alkene Hydrogenation: Catalytic Steps

(5) Ligand association

H CH2 H CH2
CH2 CH2
Ph3P Ph3P PPh3
Rh H + PPh3 Rh
Ph3P Ph3P H
Cl Cl
 WC in alkene Hydrogenation: Catalytic Steps

(6) Reductive elimination

H CH2
CH2
Ph3P PPh3 Ph3P PPh3
Rh Rh
Ph3P H Ph3P + CH3 CH3
Cl
Cl

(note: regeneration of the catalyst)

WC
IN
A
C
T
I
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