Organosilicon compounds and Silicones

Silicon is the congener of carbon, but:

• Larger
– five- and six-coordinate structures positive (because of the d-orbital participation)
• 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
Si-C bond covalent, unreactive
Si-O, Si-F very ("abnormally") strong
Si-Cl, Si-Br, Si-I reactive
Si-Si weak (!)
Si=Si and Si=C weak, very reactive

1 OrganoSilicon Compounds
 Comparison of silicon chemistry with carbon chemistry
CH4 (methane) SiH4 (silane)
bp: -161ºC bp: -112ºC
stable spontaneously flammable in air
stable, insoluble rapid hydrolysis in water
SiH4 + (n+2) H2O = SiO2∙nH2O + 4 H2
Differences:
● Electronegativity
C Si (H)
2.35 1.64 (2.79)
Si is more electropositive than C; e.g.
C―H  Si◄H
δ+ δ-
In general Si-X bond is more polar than C-X bond.

● Atomic radius of Si is bigger than C (covalent radii: 117 pm and 77 pm, respectively)
nucleophiles attack Si more easily
● Low energy empty d orbitals on Si penta-/ hexacoordination is possible
 Organosilanols and Silicones !
In the case of bifunctional chlorosilanes:
R R R
H2O - H2O
Cl Si Cl HO Si OH Si O
R R R n
Organo-chlorosilanes, RnSiCl4-n, rapidly chains, rings
hydrolyse to RnSi(OH)4-n which are - H2O
condensating, e.g.:
driving force: ESi-O>ESi-Cl R
Si O
R

Preparation of organosilicon compounds

Chlorosilanes, RnSiCl4-n (n=1-3), are of high account which are also important
precursors themselves.

3 OrganoSilicon Compounds
 Silicones applications
• 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
Silicone polymers have a range of structures and uses. Their
properties depend on the degree of polymerization and crosslinking,
which are influenced by the choice and mix of reactants,
and the use of dehydrating agents such as sulfuric acid and elevated
temperatures. The liquid silicones are more stable than hydrocarbon
oils. Moreover, unlike hydrocarbons, their viscosity
changes only slightly with temperature. Thus silicones are used
as lubricants and wherever inert fluids are needed, for example
in hydraulic braking systems. Silicones are very hydrophobic
4 OrganoSilicon Compounds
 applications
and are used in water-repellent sprays for shoes and other items.
The lower molar mass silicones are essential in personal-care
products such as shampoos, conditioners, shaving foams, hair
gels, and toothpastes, and impart to them a ‘silky’ feel. At the
other end of the spectrum of delicacy, silicone greases, oils, and
resins are used as sealants, lubricants, varnishes, waterproofing,
synthetic rubbers, and hydraulic fluids.

5 OrganoSilicon Compounds
 The Si-O-Si bond

• Si-O-Si flexible
Is also seen in structures of SiO2
• No dp-pp bond !!!!

Ph3COCPh3 Ph3SiOSiPh3
ÐCOC = 128° ÐSiOSi = 159°

6 OrganoSilicon Compounds
 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
• R3Si often behaves like a "large hydrogen"Reactions with Si-C bond fission
Not only the fissions of homolytic type do not undergo readily but also the heteroytic
ones (low polarity of Si-C bond).
However, for instance, in R3SiR’ compounds there is a good correlation between the
aptitude of the Si-C(R’) bond breaking and the C-H acidity of the parent R’H compound
(R3Si-C≡CR desilylates easily)!

7 OrganoSilicon Compounds
 Metathesis reactions Organosilicon compounds
Reactions in which two compounds react to form two new Synthesis
compounds, with no changes in oxidation number. Reactions in which the
ions of two compounds exchange partners.
1. Direct synthesis
– Si is not electropositive enough for unassisted direct synthesis
– An Si/Cu alloy works better:

RCl + Si/Cu  R2SiCl2 + RSiCl3 + R3SiCl + ...

„Direct” synthesis (Rochow-Müller) used in industry:
2. Metathesis Reactions (Methods mainly used in lab)
a) with alkyl lithium to form tetra alkylsilanes RLi
SiCl4 R4Si
b) with Grignard reagent
c) With reducing agent
3. Hydrosilylation
(hydrosilylation forms anti Markovnikoff regioselectivity)
Allyl compound undergo anti Markovnikoff addition with HSiCl3
SiCl3
HSiCl3 + R R
The above reaction can be catalyzed/initiated by light, free radicals, many transition
metal compounds.

8 OrganoSilicon Compounds
 Silylating agents
Silylation: H→SiR3 (usually SiMe3) exchange.
Principally the silylation of organic compounds having mobile H atom (carboxylic acids,
phenols, alcohols, thiols, amines, amides, carbohydrates, etc.) is of great importance.
The silylation reaction:

The application fields of the silylation:

• enhancing volatility (GC, MS),
• attaching protective and/or activating group to
organic compounds (chemical syntheses),
• hydrophobisation (silanisation), etc.

More frequently used silylating agents:

9 OrganoSilicon Compounds