OrganoSilicon Compounds

Peter H.M. Budzelaar

Organosilicon compounds
Silicon is just like carbon, but:
Larger
five- and six-coordinate structures positive

More electropositive
easier attack by nucleophiles

Does not want to form multiple bonds

SiO2 vs CO2

Organo Ge etc ... compounds: slow transition to more typical metal

chemistry; MII becomes more stable for Pb

OrganoSilicon Comp

Bonds to silicon

Si-C
Si-O, Si-F
Si-Cl, Si-Br, Si-I
Si-Si
Si=Si and Si=C

bond covalent, unreactive

very ("abnormally") strong
reactive
weak (!)
weak, very reactive

OrganoSilicon Comp

Silicones !
R
Cl

Si Cl

H2O

R
HO Si OH

- H2O

R
Si O
R

- H2O
R
Si O
R

OrganoSilicon Comp

Silicones
Based on strong -Si-O- backbone
a pure -Si-Si- backbone would be weak

"Slick"
Viscosity change little with temperature
silicone oil

Easy chemical modification and/or attachment to a surface

Silan
Silylation of GC column surfaces

OrganoSilicon Comp

The Si-O-Si bond

Si-O-Si flexible
Is also seen in structures of SiO2

No d-p bond !!!!

Ph3COCPh3
COC = 128

Ph3SiOSiPh3
SiOSi = 159

OrganoSilicon Comp

Chain folding - silicones vs alkanes

At low temperatures, both alkanes and silicones prefer to form
extended chains
At higher temperature:
For alkanes, the main change is formation of "gauche defects",
i.e. partially folded chains.
Reduces contacts between chains, lowers viscosity

For silicones, a wider range of Si-O-Si angles will occur, mainly

around 180, resulting in more extended chains
Increases contacts between chains
Counteracts the "normal" viscosity decrease, so viscosity stays nearly
constant
Very useful for high-temperature synthetic lubricants

OrganoSilicon Comp

Synthesis
Direct synthesis
Si is not electropositive enough for unassisted direct synthesis
An Si/Cu alloy works better:

RCl + Si/Cu

R2SiCl2 + RSiCl3 + R3SiCl + ...

Metathesis
SiCl4

RLi

R4Si

Hydrosilylation
HSiCl3 + R

SiCl3

Catalyzed/initiated by light, free radicals, many transition metal compounds.

OrganoSilicon Comp

Reactivity
Nucleophilic attack
Me3SiPh + F

Me3SiF + "Ph "

Electrophilic attack (on C!)

Me3SiPh + H

SiMe3 H2O
H

With halogens
Si

X2

Si

X + X C

R3Si often behaves like a "large hydrogen"

OrganoSilicon Comp

Sterics down group IV

Ph4C

Ph4Si

Ph4Sn

Ph4Ge

Ph4Pb

OrganoSilicon Comp

Higher coordination numbers

O

Ph4Si
4-coordinate

Ph3SiF25-coordinate
Ph2Si(tropolonate)2
6-coordinate

OrganoSilicon Comp

Maybe not useful, but certainly beautiful

C6(SiMe2OMe)6

OrganoSilicon Comp