Main-Group Organometallics

M+ - C-

susceptible to nucleophilic attack carbanionic in character

susceptible to attack by electrophiles

Stability – M-C is weak compared to M-N, M-O or M-Hal  use for organometallics
in synthesis

M-C bond energies – cover wide range

within a main-group

decrease with increasing

atomic number
 Main-Group Organometallics
Lability – thermal decomposition Pb(C2H5)4 Pb + C2H5•

 Pb, EtH, C2H4, C4H10….

-elimination

 
R2C CR2 R2C CR2
M H + R2C CR2
M H M H

Facilitated by vacant orbital at metal to accommodate metal-hydrogen bond pair

(Group I-III)

Stabilisation by adduct formation of Lewis base e.g. (bipy)BeEt 2

BeEt2 inflames, (bipy)BeEt2 stable 10-15 min in air

 Main-Group Organometallics

Reactivity towards O2 and H2O – highest for organometallics with free electron pair,
low lying empty orbitals and/or high polarity of M-C
bond

InMe3 pyrophoric/hydrolysed – vacant orbital on In, moderate bond polarity

SiMe4 inert/not hydrolysed – Si shielded well, low bond polarity

Reactivity of M-C bonds may also be controlled by use of sterically demanding

substituents, e.g., (Me3Si)3C, mesityl  kinetic stabilisation

c.f. Zn(CH3)2 Zn{C(SiMe 3)3}2

Pyrophoric, explodes with water Stable in air, steam
 Main Structural Types of Organometallic
Compounds

metals with a strong tendency to form

Li Be alkyl- or aryl-bridged species; B C N O F
1.0 1.6 covalent, multicenter bonds 2.0 2.5 3.0 3.4 4.0
Na Mg Al Si P S Cl
0.9 1.3 1.6 1.9 2.2 2.6 3.1
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
0.8 1.0 1.3 1.5 1.6 1.6 1.6 1.8 1.9 1.9 1.9 1.7 1.8 2.0 2.2 2.6 2.9
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
0.8 1.0 1.2 1.3 1.6 2.1 1.9 2.2 2.3 2.2 1.9 1.7 1.8 1.8 2.0 2.1 2.6
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At
0.8 0.9 1.1 1.3 1.5 2.3 1.9 2.2 2.2 2.3 2.5 2.0 1.6 1.9 2.0 2.0 2.2

metals that transition metals metals and metalloids that non-metals

form ionic -complexes tend to form volatile, covalent
derivatives predominate organo derivatives
mainly M-C -bonds
rarely M-C -bonds
 Synthesis

Direct Synthesis 2 M + n RX RnM + MXn (or RnMXn)

2 Li + C4H9Br C4H9Li + LiBr not for e.g. Hg or Pb

Mg + C6H5Br C6H5MgBr
2 Al + 3 MeCl Me3Al2Cl3

2 Na + Hg + 2 CH3Br (CH3)2Hg + 2 NaBr Mixed Metal

4 NaPb + 4 C2H5Cl (C2H5)4Pb + 3 Pb + 4 NaCl Synthesis

Transmetallation M + RM’ RM + M’

Zn + (CH3)2Hg (CH3)2Zn + Hg

favourable when M is higher in electrochemical

series than M’

slow
 Synthesis

Metathesis RM + M’X RX + R’M

Li Mg Al Zn Si B As P
Electronegativity: 0.98 1.31 1.61 1.65 1.90 2.04 2.18 2.19

Li4(CH3)4 + SiCl4 4 LiCl + Si(CH3)4

Al2(CH3)6 + 2 BF3 2 AlF3 + 2 B(CH3)3

Hydrometallation M-H + C C M C CH M = B, Al, Si, Zr, e.g.

(C2H5)2AlH + C2H4 (C2H5)3Al

Reverse of -elimination
 Reaction Pattern

Oxidation - potential reducing agents; for electropositive elements very strong reducing
agents
- componds of electropositive metals have unfilled valence orbitals,
or readily dissociate to fragments with unfilled orbitals - pyrophoric

Nucleophilic (carbanion) Character

-organic group at electropositive
- metal has partial negative charge
- strong nucleophile and Lewis base
- most commonly used carbanion
reagents LiR and RMgX
 Reaction Pattern

Protolysis Reaction

Et Et CH3 Et
CH3OH
Ga Et Ga O Ga OCH 3
Et Et - C2H6
Et H Et

Al2(CH3)6 + 6 C2H5OH 2 Al(OC2H5)3 + 6 CH4

Lewis Acidity – presence of unoccupied orbitals on metal, electron-deficient

B(C6H5)3 + Li(C6H5) Li[B(C6H5)4]

Al2(CH3)6 + 2 N(C2H5)3 2 (CH3)3AlN(C2H5)3

 Alkali Metal Organometallics – Method of Synthesis

Direct Synthesis - organic halide + metal

Transmetallation - using Hg organyls

Metal Exchange - PhLi + (CH2=CH)4Sn 4 (CH2=CH)Li + Ph4Sn

(good yields of vinyllithium)

Metal-Hal Exchange - BunLi + PhX BunX + PhLi (practicable only for ArX; competing
reaction Wurtz coupling)

Metallation of C-H Acid - Na + C5H6 C5H5Na + 1/2H2

 Alkali Metal Organometallics – Method of Synthesis

For heavier alkali metal organometallics – widely used method metathesis of

organolithium reagent and an alkoxide

e.g., BunLi + KOBut LiOBut + BunK

in hydrocarbons, easy to separate the MR product, e.g. BunK

CH3CH2OCH2CH3 + KC 4H9 C4H10 + K [CH-O-C2H5]

CH3

Ether Cleavage

KOC2H5 + H2C=CH2
 Organolithium Structures

Li Li Li C
CH3
CH 3

Li

CH 3 Li
Li
Li

Li

Li Li Li Li
CH3

Et2O.
Tendency to form Li
Ph
oligomers through Ph
multicentre bonds Li .OEt2
Li3 group Ph
C orbitals Li .OEt2
Et2O. Li
sp3 Ph
MeLi tetramer

MO diagram for one of the four 2e 4c bonds in R4Li4

 Organolithium Structures

ButLi tetramer Hexamer of BunLi

 Organolithium Structures

LiR Solvent Aggregation

Li OEt2
MeLi thf, Et2O tetramer
Ph
Me2CH2CH2NMe2 (Li4 tetrahedron
(tmeda) monomer, dimer
BunLi cyclohexane hexamer
Ph
Et2O tetramer
Et2O Li
ButLi hydrocarbons tetramer Ph

thf monomer

LiCH2Ph thf, Et2O monomer

Ph
LiC3H5 (allyl) Et2O columnar structure Li OEt2
thf dimer
 Organolithium Structures

Degree of association strongly dependent on nature of solvent

Affects structures and reactivity by increasing polarity of Li-C bond

Rates of metallation by PhCH2Li exceed those of CH3Li by factor of 104, although

CH3- stronger base as PhCH2-

N
C6H12
(n-C4H9Li)6 6 Li+ C4H9-
6 tmeda
N

Complexation of Li+; polarisation of Li-C bond;

carbanionic character of butyl group increased

 Reactions of Organolithium Compounds

Metallation of C-H, N-H, O-H acids R-Li + E-H R-H + E-Li

when E-H is stronger acid than R-H

H H
Li+
BunLi
+ BuH

NH2
BunLi
NHLi

+ BuH

Reactions with Main-Group and Transition-metal Halides

RLi + M-X M-R + LiX

 Reactions of Organolithium Compounds

Additions to Multiple Bonds

R'Li
R' R' hydrolysis R'
hydrolysis
R C N C NLi C NH C O
R R R

O OLi O
RLi hydrolysis
H C R C NR'2 R C
H
NR'2 H

CO CO CO

OC CO OC CO OC CO
LiR [(CH 3)3O]BF 4
W W W
OC CO OC CO OC CO
CO C C

R O-Li+ R OCH3
 Radical Anion Salts

M + ArH M+ + ArH . 2 M + ArH 2 M+ + ArH2-

Na + C10H8(thf) Na[C10H8](thf) sodium naphthalenide

(Me5C5)2SiBr2 K, anthracene
- 2 KBr
Si
 Radical Anion Salts

K
2 C8H8 2 C8H8. C8H8 + C8H82-
- K+

2-

nonplanar
4n electrons planar planar
antiaromatic (4n+1) -electrons (4n+2) -electrons
aromatic
 Organomagnesium Compounds

Direct Synthesis Mg + RX RMgX(OR’2)n

Transmetallation Mg + R2Hg R2Mg + Hg

Metallation R-CCH + EtMgBr R-CCMgBr + EtH

Schlenk Equilibrium 2 RMgX + 2 dioxane R2Mg + MgX2(dioxane)2

 Organomagnesium Compounds

R. RMgX
RX

Formation
RX R. . MgX

Mg Mg Mg

Activation of Mg: I2, CCl4, 1,2-dibromoethane

Riecke magnesium:
K, thf
MgCl2 Mgactive
C8H17F
C8H17MgF 89%!
r.t., 3 h
 Organomagnesium Compounds

Schlenk equilibrium

L X L R X L
Mg Mg 2 RMgX R2Mg + MgX2 Mg Mg
R X R R X L
III I II IV

L = solvent with donor properties, usually ether

Dominant forms: I – ether solution of low concentration

II – in Et3N, with dioxane only MgR2 in solution,

precipitation of MgCl2(dioxane)2

III and IV – in higher concentration and with more basic thf

 Organomagnesium Compounds

Structure
Generally polymeric/oligomeric structures, where halide (2e2c) bridges are preferred
over 2e3c alkyl bridges

Mg

Al Al

Exception: [(Me3Si)3C]Mg is monomeric

due to bulky substituents
 Organomagnesium Compounds
Reactivity
O
RMgX + R'CN R C R'
Use in organic synthesis, e.g.
RMgX + R'CHO RR'CH-OH

Alkylating/arylating reagents for main group and transition metals halides

CH3MgX

SbCl3 + 3 CH3MgX (CH3)3Sb

- 3MgXCl

compared to LiR, RMgX reagents - less reactive (do not form ate complexes)

- less reducing with transition metal halides

 Organomagnesium Compounds

Magnesium-’ate-complexes’ MxMgyRz (M = group 1,2 and 13);

the less EP metal usually in ‘ate-complex’ anion

Et2O MeLi
MgMe2 + LiMe LiMgMe 3(Et2O)n
tmeda
lithium magnesiate
 Organometallics of Calcium, Strontium and Barium

Highly reactive due to predominantly ionic character of metal-ligand bond

increased lability complicates synthetic access; unstable and/or sparingly soluble

Synthesis

Transamination M[N(SiMe3)2]2 + 2 HR MR2 + 2 HN(SiMe3)2

Direct metallation 2 HR + activated M MR2 + H2

Transmetallation/ HgR2 + activated M MR2 + Hg

Metal exchange
2 LiR + M(OR)2 MR2 + 2 LiOR

M[N(SiMe3)2]2 + 2 LiR MR2 + 2 LiN(SiMe3)2

M[N(SiMe3)2]2 + 2 LiCH2Ph M(CH2Ph)2 + 2 LiN(SiMe3)2

MI2 + 2 LiCp* Cp*2M + 2 LiI

 Organometallics of Calcium, Strontium and Barium
Most intensively studied are the cyclopentadienyl systems

Magnesocene is useful reagent for introduction of C 5H5 groups

M ,
MCp*2
Cp2Mg Cp*2Ca
Mg 180
Ca 154
Sr 149
Ba 148

Sterically should be parallel, however explained

by polarisable ion model – bending due to dipole induced  M2+ 
on large central cation (also Yb(II), Eu(I) analogues) –
maximises electrostatic bonding
 Organometallics of Calcium, Strontium and Barium

purely -bonded ligands - scarce

[Ca{CH(SiMe3)2}2(1,4-dioxane)2] Ca[C(SiMe3)3]2

CCaC 150

Lappert, 1991 Eaborn/Smith, 1997

Tris(trimethylsilyl)methylmagnesium and -calcium
 Organoaluminium Compounds
Synthesis
Transmetallation 3 Ph2Hg + 2 Al 2 AlPh3 + 3 Hg

Metathesis (RLi or RMgX) AlCl3 + 3 ButLi AlBut3 + 3 LiCl

Hydroalumination 3 RCH=CH2 + AlH3.OEt2 (RCH2CH2)3Al.OEt2

Direct synthesis 2Al + 3RX 2 R3Al2X3 ‘sesquihalide’

Properties

Alkyls are usually colourless liquids that react violently with air and water; short
chain lengths pyrophoric

Lewis acidic (6 valence electrons) – marked effects on structure and reactivity

 Organoaluminium Compounds

Applications

Aufbau reaction (growth reaction) - multiple insertion of ethylene into the Al-C bond
e.g. AlC2H5 + C2H4  AlC4H10 etc (Ziegler)
- produces 1-alkenes and (after reaction with
dioxygen and hydrolysis) unbranched C 16 – C20
primary alcohols for detergent industry

Catalytic dimerisation of propene – basis for production of isoprene

(-synthetic rubber)

Olefin polymerisation – Ziegler-Natta low-pressure process with mixed

catalysts like Et3Al/TiCl4
 Organoaluminium Compounds

Catalytic dimerisation of propene

C
CH2=CHCH3
Pr3Al Pr 2AlCH2CHMePr

CH2=CHCH3

Pr2AlH + CH2=CMeCH2CH2CH3

cracking

CH2=CMeCH=CH2 + CH4

isoprene
 Organoaluminium Compounds

Structure and bonding Al2(CH3)6

C
a C b
H3
 214 pm
H3C C
 CH3
Al 75º Al 109.5º Al Al Al Al 120º
123º
Al(sp3) Al(sp2)
H3C CH3
C 197 pm
H3
C
260 pm
C
C Al C
Al
Al Al C Al Al Al Al
C

(2e3c) + (2e3c) (2e2c) (2e4c)

+

Al2Cl6 d(Al-Al) 340 pm with Al-X-Al bridges

Σ rcov Al = 252 pm [rcov(Al) = 146 pm]

 Organoaluminium Compounds
Structure and bonding Al2(C6H5)6

114º a 120º c 109.5º

sp2 sp3
196 pm sp3
218 pm
Ph Ph
Al 76º Al 115º Al Al Al Al
Ph Ph

270 pm
-C6H5 = -C6H5 =
 Organoaluminium Compounds

Association in solution – Al-C-Al bridging persists in non-polar solvents with

fast Al-Me exchange
50 C + 20 C
R b R
0.5 6.5 0.3 R R R R
Al Al Al Al
R R R
R* R R*
a

R
R R R
R R*
Al Al Al Al
R R
R* R R
R

a R = Me b R = Ph
 Organoaluminium Compounds

R2AlX and RAlX2 (X = halide) are most conveniently prepared by redistribution

of trialkyls and trihalides in correct stoichiometry. Reactions occur readily at RT.

2 R3Al + AlCl3 3 R2AlCl Me X Me

Al Al
R3Al + 2 AlCl3 3 RAlCl2 Me X Me

usually oligomers, formed by Al-X-Al bridging

(interaction with heteroatom lone pair favoured over Al-C-Al)

Al-Me-M bridges also formed with other acidic metal centres, e.g.

AlMe3 + Cp2Yb
 Organoaluminium Compounds
Reactivity
Organoaluminium compounds are hard acids and readily form adducts with bases
such as thf and amines

Mes3Al + thf

Reactions with protic reagents gives access to wide variety of organoaluminium

compounds

AlR3-n + n R’OH R3-nAl(OR’)n

 Organoaluminium Compounds

Formation of ‘ate-complexes’ AlR3 + LiR Li[AlR4]

Carbalumination

+
CH2=CHR H2C CHR H2C CHR
1/2 (Et3Al)2 Et3Al
Et2Al Et Et2Al Et

Hydroalumination
H2 C CHR

Et2Al H
 Organometallics of Ga, In and Tl
Synthesis

R3M may be prepared by same methods as for R 3Al – metathesis or RLi/MgX with MX3

- transmetallation with organomercurials

Halides RnMX3-n most readily prepared by redistribution reactions

Structure R3Ga and R3In monomeric Lewis acidity less than that of Al
Me3Ga very important ion semiconductor industry more inflammable
than dimeric Me3Al

Reactivity Less reactive than aluminium compounds so possible to get e.g.

Me2GaOH easily
 Organometallics of Ga, In and Tl

Cl In
R X R
Ga Ga In Cl [Me2InCl]n
R X R
Cl In

in R2MX compound the larger In can adopt coordination numberes > 4

– leads to coordination polymers in solid state
 Group 14 Organometallics
Common oxidation state of +4 with increasing stability of +2 as group is descended

In contrast to group 13 derivatives R4M derivatives show lower bond polarity of the E-C bond,
have an octet configuration and reactivity towards nucleophiles is diminished,
ie. ER4 species are usually water-stable and often air-stable

E Thermal stability Bond energy Bond length Bond polarity EN

E(E-C) in kJ/mol d(E-C) in pm E+ - C-

C 358 154 2.5

Si 311 188 1.9
Ge 249 195 2.0
Sn 217 217 1.8
Pb 152 224 1.9
 Group 14 Organometallics

Chlorination of ER4 species: for E = C and Si chlorination of organic part but for
E = Ge, Sn or Pb cleavage of the E-C bond

+ -
E C Availability of empty nd orbitals at E renders associative
Mechanism of substitution possible by extending
Nu El the CN to 5
nucleophilic electrophilic
attack attack
Successive replacement of R by more EN groups X in
RnEX4-n increases affinity of E for attacking nucleophiles

Me4Sn inert towards H2O and [SnMe6]2- unknown, but

Me2SnCl2 hydrolyses and [Me2SnCl4]2- can be prepared
 Organosilicon Derivatives
Preparation
Metathesis with RLi, RMgX or R3Al SiX4 + nLiR SiX4-nRn + nLiX

3 SiX4 + 4 AlR3 3 SiR4 + 4 AlX3

Hydrosilylation (anti-Markovnikov) R3SiH + CH2=CHR R3SiCH2CH2R

Industrially, prepared by 2 RCl + Si/Cu R2SiCl2 (ca. 70%)

Rochow process

Organosilanes - properties

R4Si are H2O and O2 stable because of low bond polarity, heterolytic cleavage does
not occur readily

Si-C bonds are thermally stable and do not decompose before ca. 700ºC

Leads to use in silicon polymers from hydrolysis of chlorosilanes – now a very mature
industry

Chlorosilanes are commonest precursor for wide range of organosilanes

 Organosilicon derivatives

R2SiCl2 + H2O / catalyst  (R2SiO)n + ClR2Si(OSiR2)nOSiR2Cl

cyclics linear
D4 predominates

Mainly R = Me 106 tonnes/year

Si O Si O

O Si O Si

• Thermal stability up to 350 C Unzipping rate less when R = Ph

• Low temperature coefficient of viscosity Tg < 120 C
SiOSi ca 145 C easy rotation
• Good insulator
• Hydrophobicity coatings, waxes, sealants
• Many variations in pendant groups - copolymers
 Organosilicon Derivatives
Selected Reactions of organohalosilanes
(R3Si)2O

-H2O

R3SiOH
-NH3
R3SiR' R3SiNH2 (R3Si)2NH
H2O NH3
R'Li

LiAlH4 H2S -H2S

R3SiH R3SiCl R3SiSH (R3Si)2S

Li R'OH
RSNa

R3Si-SiR3 R3SiOR'
R3SiSR
 Organo(germanium), -tin and (-lead) derivatives, RnMX4-n

Preparation of R4M most commonly by metathesis of MX 4 with RLi, RMgX and R3Al
derivatives
other methods similar to those employed for organosilanes

Preparation of the most important routes involve redistribution of tetraalkyl

RnMX4-n derivatives with tetrahalides; in contrast to group 13 derivatives
these reactions generally involve elevated temperatures
(ca. 170 ºC)
Structure/ R4Sn – simple tetrahedral (sp3) coordination is encountered in
properties tetraalkyls which are air/moisture stable

R3SnX – with more electronegative groups attached the Lewis acidity

increases and higher coordinate derivatives result from coordination
by bases in absence of external bases polymeric structures are
common Cl
Me Me Me
R Me Sn Me Me
F
Me Sn Sn
N Sn
Sn F F Me
R Me Me Me
R Me

Me3SnF, 1D polymer with tbp Sn (5 coordinate)

 Organotin Derivatives

Selected Reactions of organohalostananes

(R3Sn)2O
R3SnOH
R3SiR' R3SnOR'
H2O
R'Li R'OH, R3N

LiAlH4 LiNR'2
R3SnH R3SnCl R3SnN'R 2

NaC5H5
Na

NaMn(CO)5
R3Sn-SnR 3 R3SnC5H5
R3SnMn(CO) 5

Compounds containing R3Sn are toxic and must be handled with great care
 Organotin Hydrides
LiAlH4, Et2O
RnSnX4-n RnSnH4-n

Hydrostannation Sn H + A B Sn A B H

in absence of Lewis acids or radical forming reagents polar double bonds like C=O or
C=N are not attacked
well-suited for chemoselective hydrogenation of activated C=C bonds

1. cat. (Ph3P)4Pd,
H H O thf, 20 ºC H 2 H2 O
Ph C C C + Bun3SnH Ph C C C
H 2. H2O H

in presence of AIBN 1,4-addition to conjugated dienes occurs

AIBN
Et3SnH + CH2=CH-CH=CH2 Et3SnCH2-CH=CH-CH3
 Organotin Hydrides

Hydrostannolysis Sn H + X Y Sn Y + HX

R3SnH transfer
R3Sn-H + MeCOOH R3SnOOCMe + H2 H-
4 R3Sn-H + Ti(NR'2)4 (R3Sn)4Ti + 4 HNR'2 H+
2 R3Sn-H + R'2Hg (R3Sn)2Hg + 2 R'H H.
-Hg
R6Sn2
R = Me, -10 ºC
R = Ph, +100 ºC

R'3Sn-H R'3Sn. + H. (start)

R'3Sn. + RX R'3SnX + R.
(propagation)
R. + R'3SnH RH + R'3Sn.

low polarity of Sn-H bond R3SnH may act as a source of H-, H+ or H.,
depending on nature of attacking agent
 Organotin Hydrides

But3SnH But3SnH
Br
h h
Me2 Br2 Me2 Me2 H2

most convenient methods for conversion R-X to R-H

e.g., selective reduction of geminal dihalides in presence of other sensitive
groups