Hydrogen Bonding to Silanols

Ian Baxter, Lisa D. Cother, Carole Dupuy, Paul D. Lickiss, Andrew J. P. White
and David J. Williams
Department of Chemistry, Imperial College of Science, Technology and Medicine,
London SW7 2AY, UK
Abstract
Silanols are compounds analogous to alcohols and contain one or more SiOH groups.
Such functional groups are ubiquitous in nature, for example in silicic acid, Si(OH)
4
,
found in low concentration in the aqueous environment, and on the surface of silicate
rocks. The silanol group is also important in a variety of industrial situations such as
the manufacture of silicones, sol-gel processes, and as silane coupling agents for use
in the functionalisation of surfaces. One of the most important features of the
chemistry and structure of silanols is the high acidity of the group which means that
they tend to form strong hydrogen bonds both to themselves and to organic molecules
containing suitable hydrogen bonding sites. Silanols thus form a wide range of
hydrogen bonded structures ranging from simple dimers, through various types of
chain and sheet, to extended three-dimensional networks. This article will describe the
variety of structures found and will concentrate on the hydrogen bonded complexes of
arylsilanols, for example, Ph
3
SiOH and (HOPh
2
Si)
2
O. Such species have been found
to form complexes such as (HOPh
2
Si)
2
O.TMEDA and [(HOPh
2
Si)
2
O]
4
.[Et
2
NH]
2
that
can be structurally characterised. These hydrogen bonded complexes can be seen as
potential models for the interaction between the inorganic world of silicate surfaces
and the world of organic functional groups. This area has become of greater relevance
recently since it has been found that silicones are broken down to low molecular
weight silanols in the environment.

Introduction
Silanols are compounds containing the Si-OH group and are thus analogous to the
much more well known alcohols. There are, however, despite their close apparent
similarities many differences between the two types of compound. For example, it is
easier to prepare silanediols, R
2
Si(OH)
2
and silanetriols, RSi(OH)
3
than their carbon
analogues, and, unlike alcohols, the silanol group has a strong tendency to undergo
self condensation reactions to give compounds containing the siloxane, Si-O-Si,
linkage. Such condensation reactions mean that silanol containing species are
important industrial intermediates, for example, in the silicone industry
polycondensation of silanols leads to the formation of silicones, and the hydrolysis of
alkoxysilanes leads to silanols as intermediates in sol-gel processes and in surface
functionalisation using silane coupling agents. In addition, the Si-OH group is an
important reactive site on the surface of silicate rocks and minerals and is found
widely distributed at low concentration in water as Si(OH)
4
. Recent work has also
shown that the breakdown of silicone polymers in the natural environment leads to the
formation of low molecular weight silanols such as Me
2
Si(OH)
2
and
(HOMe
2
Si)
2
O.
1
This could have potential environmental implications as silicones are
now very widely spread throughout the natural world.
One of the most important aspects of silanol chemistry is the relatively high acidity of
the group. Various IR spectroscopic and titration studies have shown that the relative
order of acidities for silanols and alcohols is arylsilanols > alkylsilanols >
arylcarbinols > alkylcarbinols.
2
The high acidity, coupled with the relatively high
basicity,
2
of the silanol group means that silanols have a strong tendency to form
hydrogen bonds both between themselves and to other species containing suitable
hydrogen bonding sites. Hydrogen bonding between silicone derived organosilanols,
and organic compounds in the environment or silicate surfaces may play an important
role in the complete breakdown of silicones to inert inorganic materials.
Hydrogen Bonded Complexes of Silanols
The wide range of solid state structures adopted by silanols has been reviewed,
2
the
work described below, however will concentrate on more recent studies of compounds
in which a silanol forms a hydrogen bonded complex with a suitable organic
molecule. The first work in the field was carried out over thirty years ago when
Prescott and Selin showed that the disiloxanediol, (HOPh
2
Si)
2
O, formed solid
complexes of 1:1 stoichiometry but of unknown structure, with Et
2
NH, Et
3
N, PhNH
2
,
(Me
2
NCH
2
)
2
and pyridine, and that the trisiloxane (HOPh
2
SiO)SiPh
2
formed a 1:1
complex with pyridine.
3
More recently, structural studies have been carried out on a
variety of complexes such as [(HOPh
2
Si)
2
O]
3
.(C
4
H
4
N
2
),
4
which shows both silanol-
silanol and silanol-amine hydrogen bonds, 1, and the pyridinium hydrochloride
complex (HOPh
2
Si)
2
O.C
5
H
5
N.HCl, 2.
5
Intramolecular SiOH
...
N hydrogen bonds are
formed in the sila-drug sila-difenidol
6
but other sila-drugs such as sila-
pridinol,
7
Me
2
N(CH
2
)
2
SCH
2
SiPh
2
OH,
8
(2-morpholino)SiPh
2
OH,
9
(3-
morpholino)SiPh
2
OH,
10
(C
5
H
10
N)(CH
2
)
2
OCH
2
SiPh
2
OH, 3,
11
sila-procyclidine
12
and
sila-biperidin
13
form intermolecular SiOH
...
N hydrogen bonds to give dimeric or chain
structures. A more detailed description of these and related structures can be found in
reference 2.


The complexes formed by silanols may be highly specific to the structure of the
hydrogen bonded molecules. For example, the liquid trialkylsilanol Bu
t
Me
2
SiOH
readily forms a solid hemihydrate [Bu
t
Me
2
SiOH]
2
.H
2
O but it does not form an
complex with low molecular weight alcohols, and the related silanols Pr
i
Me
2
SiOH, t-
hexylMe
2
SiOH, and Ph
2
Bu
t
SiOH do not seem to form complexes with
water.
14
Similarly, Ph
3
SiOH forms a 4:1 complex, [Ph
3
SiOH]
4
.EtOH, with ethanol
even in the presence of a large excess of water, methanol or
propanol.
15
Triphenylsilanol also forms hydrogen bonded complexes with ethers, for
example a 2:1 complex forms with 12-crown-4
16
and a 4:1 complex with dioxane.
17

One of the problems in trying to understand the important factors that govern the
formation of well defined silanol complexes is that there are many situations where
attempts to form a particular complex lead to silanol condensation reactions. For
example, in most instances the addition of an amine to methylsilanols such as
(HOMe
2
Si)
2
O leads to the formation of siloxanes rather than hydrogen bonded
complexes as the condensation of silanols is catalysed by both bases and acids. This
has led to most of the successful studies being carried out using the more bulky (and
hence more stable) aryl silanols, although Selin was able to show that the
unsymmetrical disiloxane HOPh
2
SiOSiMePhOH did form stable complexes with both
tributylamine and pyridine.
18
Even for arylsilanols condensation reactions may be
troublesome for example treatment of (HOPh
2
Si)
2
O with either Bu
n
NH
2
or n-
octyl
2
NH leads to new siloxane bond formation.
19

In spite of the problems associated with condensation reactions and with the apparent
highly specific structural requirements for the formation of well defined compounds
that can readily be isolated we have been able to prepare and structurally characterise
a range of novel silanol complexes. The TMEDA complex (Ph
3
SiOH)
2
.TMEDA
comprises discrete centrosymmetric units in which each Ph
3
SiOH molecule bonds to a
single nitrogen of the TMEDA molecule while, surprisingly, in Ph
3
SiOH.tris(2-
aminoethylamine) which contains four potential hydrogen bonding sites, only one is
used, the silanol interacting with a single NH
2
group.
20
Triphenylsilanol also forms an
interesting complex, (Ph
3
SiOH)
2.
18-crown-6.(H
2
O)
2
, in which the silanol groups
hydrogen bonds to the water molecules which, in turn, hydrogen bond to the ether
ring.
20
The structure of the dioxane complex (HOPh
2
Si)
2
O.dioxane is also an infinite
chain similar to that in (Ph
3
SiOH)
2
.TMEDA.
20
We have now extended the range of
hydrogen bonded complexes and three new compounds are described below.
The crystalline complex (HOPh
2
Si)
2
O.TMEDA is readily formed after addition of
hexane to a toluene solution of the silanol and the amine.
Show Hydrogen Bonds
The disiloxane and the TMEDA are positioned on crystallographically independent
inversion centres. The disiloxane linkage is linear and the OH groups are anti. The Si-
O bonds in the siloxane linkage and the silanol groups are 1.602(2) and 1.599(4)
respectively. The silanol and the amine molecules are linked via OH
...
N hydrogen
bonds (O
...
N, H
...
N, 2.73 and 1.84 , OH
...
N, 169 [ring]) to form a polymer chain in the
crystallographic 1 bar1 0 direction. There are small distortions from optimal
tetrahedral geometry at silicon, with angles ranging between 105.8(2) and 112.8(2)
[ring].
The arrangement is similar to that found for (Ph
3
SiOH)
2
.TMEDA except that in the
Ph
3
SiOH complex the presence of only one SiOH group in each silanol molecule
means that discrete units are formed rather than infinite chains.
20
A linear siloxane
linkage has also been found in [(HO)
2
Bu
t
Si]
2
O which forms hydrogen bonded
sheets, 4 with alternate Bu
t
groups above and below the plane of the sheet.
21
The
structure of (HOPh
2
Si)
2
O itself in the solid state comprises infinite hydrogen bonded
chains with the arrangement shown, 5.
22
The O
...
N hydrogen bonded distance in
(HOPh
2
Si)
2
O.TMEDA is in the range found for similar interactions in the sila-drugs.
2



The amine complex [(HOPh
2
Si)
2
O]
4
.[Et
2
NH]
2
can be prepared in a similar way to the
TMEDA complex above, the molecular struture and the detail of the hydrogen
bonding are shown in the figures.
Show Hydrogen Bonds
The X-ray analysis reveals the formation of a 4:2 complex between the siloxanediol
and the Et
2
NH. The asymmetric unit contains four crystallographically independent
silanol molecules of similar conformations, each having a pseudo gauche relationship
between their hydroxyl groups with respect to the associated Si
...
Si vectors (torsion
angles O-Si
...
Si-O ranging between 37 and 59 [ring]). The siloxane Si-O-Si angles are
in the narrow range 140.5(4) to 145.5(4) [ring] and their Si-O distances range between
1.607(5) and 1.649(5) ; the Si-OH distances range between 1.586(5) and 1.635(6) .
The 4:2 complexes in the crystal exist as discrete hydrogen bonded units. Pairs of
silanol molecules are linked via OH
...
O hydrogen bonds (O
...
O distances ranging from
2.66 to 2.75 ). These pairs are linked via a combination of OH
...
N and NH
...
O
hydrogen bonds (OH
...
N, 2.82 , NH
...
O, 3.14 ) to one of the Et
2
NH molecules. The
second Et
2
NH molecule is linked via an OH
...
N hydrogen bond to just one hydrogen
bonded pair of silanol molecules (OH
...
N, 2.70 ), the amino hydrogen atom of this
second diethylamino molecule being directed back into the 4:2 complex forming a
NH
...
[pi] interaction with one of the phenyl rings on an adjacent silanol molecule
(H
...
[pi], 2.66 ). Because of the inwardly directing nature of all of the hydrogen
bonding interactions, the 4:2 complex presents an essentially hydrophobic exterior
and is only involved in weak edge to face interactions between peripheral phenyl rings
of adjacent complexes. The discrete units formed by this complex are in contrast to
the more usual variety of chain structures formed by the siloxanediols (HOR
2
Si)
2
O (R
= Me, Et, Pr
n
, Pr
i
, Ph)
2
and several of the sila drugs as described above.
2

A third amine complex, [(Me
3
Si)
3
CSiPh
2
OH].TMEDA, can be isolated from an ether
solution of the amine and the silanol. The X-ray analysis reveals a 2:1 complex, the
TMEDA being positioned about a crystallographic inversion centre.
Show Hydrogen Bonds
The two silanol units are linked to the TMEDA via OH
...
N hydrogen bonds (O
...
N,
H
...
N, 2.75, 1.89 , O-H
...
N, 158 [ring]). There are small departures from tetrahedral
geometry at the quaternary carbon centre with angles ranging 106.4(1) to 113.1(1)
[ring]. The C-Si distances range between 1.906(3) for the SiOH silicon to 1.944(3)
to one of the SiMe
3
groups. The Si-O distance is 1.628(2) . Inspection of the
packing shows the complexes to exist as essentially discrete units, there being no
intemolecular [pi]-[pi] or CH-[pi] interactions. The hydrogen bonding arrangement is
similar to that found for (HOPh
2
Si)
2
O.TMEDA in that the TMEDA molecules act as
bridges between the silanols, but in this case [as for (Ph
3
SiOH)
2
.TMEDA
20
] with only
a single SiOH group in each silanol molecule, discrete units rather than infinite chains
are formed. (The structure of (Me
3
Si)
3
CSiPh
2
OH itself comprises simple dimers with
only a single OH
...
OH hydrogen bond.
23
) In contrast to many organosilicon
compounds containing the sterically demanding (Me
3
Si)
3
C group, it does not, in this
case, seem to lead to any unusual structural features.
Conclusions
There are a wide range of hydrogen bonded complexes of silanols now known but it is
still difficult to predict whether a particular silanol might form a well defined complex
with an organic base and if it does so what its stoichiometry and structure might be.
The silanol hydrogen bonded complexes can be seen as models for the interaction of
the inorganic world of silicate rocks with that of the world of organic molecules.
However, much more work needs to be carried out in order to understand what the
important structural factors are, and also to use silanol molecules that model silica
surfaces more realistically, for example, the silsesquioxanes [R
7
Si
7
O
9
(OH)
3
] (R
= cyclo-pentyl, -hexyl or -heptyl)
24
which are geometrically similar to the idealised
surfaces of -crystobalite and -tridymite.
Experimental
The amine complexes of the silanols were prepared by co-dissolving the amine and
the silanol in a solvent such as toluene or ether. Hexane was then added to cause
crystallisation or the solvent was removed under reduced pressure such that
precipitation occurred. Full experimental details, together with spectroscopic and X-
ray structural details, will be published elsewhere.
Acknowledgements
We acknowledge the EPSRC for financial support of this work. We also thank the
Dow Corning Corporation for financial assistance under the EPSRC CASE scheme
and for many fruitful discussions.