From the selective cleavage of the Si-O-Si bond in disiloxanes to zwitterionic, water-stable zinc silanolates

Article abstract of DOI:10.1002/anie.200902318

Zinc salts do Si-O's: Organosilicon chemistry is crucially determined by the high stability and chemical resistance of the Si-O-Si bond. The formation and structural existence of water-stable metallasilanolates demonstrate both the possibility to cleave the Si-O-Si bond with simple zinc compounds under mild conditions as well as the existence of such molecular metallasilanolates in the presence of water.

Full text of DOI:10.1002/anie.200902318

Communications
DOI: 10.1002/anie.200902318
Siloxane Chemistry
From the Selective Cleavage of the Si-O-Si Bond in Disiloxanes to
Zwitterionic, Water-Stable Zinc Silanolates**
Christian Dꢀschlein, Jonathan O. Bauer, and Carsten Strohmann*
The high stability and relatively low reactivity of the Si-O-Si
bond in functionalized siloxanes under ambient conditions is
a fundamental property in organosilicon chemistry (such as its
high stability towards heat and radiation or its chemical
resistance).[1,2] In the course of discussions of sustainability
and environmental protection, the demand for a mild and
Scheme 1. Central unit of the thermolysin/silanediol complex (simpli-
easy cleavage of the Si-O-Si unit in siloxanes has arisen,
particularly in the context of recycling widely used silicones.
Yet only a few concrete approaches exist to date.[3]
fied): supposed silanediol structure by Juers et al. (left), in which the
[11]
À
shortened Zn O distance was attributed to hydrogen bonding, and
a possible silanolate structure with an ionic interaction (right), which
was not discussed owing to the known kinetic lability of the Si-O-Zn
fragment.
In contrast, molecular metallasilanolates have gained
increasing attention in various fields of modern chemistry,[4,5]
such as for the preparation of structurally modified silica
surfaces (artificial surface design) and as new inorganic
materials for homogeneous catalysis reactions.[6] As molec-
ular siloxane compounds containing an R3Si-O-MXn unit
(M = main-group/transition metal, X = variable) are known
to be readily hydrolyzed by water to form the corresponding
silanols or disiloxanes,[7–9] they have not been considered
relevant under aqueous conditions. This mindset has had a
critical impact not only on synthetic chemistry but also, for
instance, on the interpretation of interactions between
transition metals such as zinc and silanol units in enzymes.[10]
Juers et al. reported the characterization of the first thermo-
lysin/silanediol complex by X-ray structural analysis.[11,12] In
that case, a silanediol inhibitor was bound to the zinc ion of
the metalloprotease thermolysin through both hydroxy
groups of the silicon. An observed, preferential interaction
of the enzyme with one of the oxygen atoms of the silicon unit
was referred to as a particularly strong hydrogen bond of one
of the hydroxy groups (A, Scheme 1). A potential silanolate
structure (B, Scheme 1) has not been discussed owing to the
known sensitivity of such moieties under aqueous conditions.
As part of our studies on aminoalkyl-substituted
silanes,[13,14] we report herein the unexpected isolation and
the characterization of highly stable molecular zinc silano-
lates containing an Si-O-Zn unit in the presence of water.
Their formation by treatment of functionalized disiloxanes
with simple zinc(II) salts demonstrates an easy and hitherto
unconsidered method for the selective cleavage of the strong
and unreactive Si-O-Si bond.
1,3-bis(piperidinomethyl)tetramethyldisiloxane (1) was
chosen as reactant for our studies concerning the cleavage
of the Si-O-Si unit as it is a simple model system for methyl-
substituted silicones and to ensure full a condensation of the
silanol precursor. Its preparation was accomplished in a two-
step synthesis. First, controlled hydrolysis of (chloromethyl)-
dimethylchlorosilane gave the corresponding intermediate
silanol, which directly condensed under elimination of water
to yield 1,3-bis(chloromethyl)tetramethyldisiloxane (2). The
subsequent treatment of 2 with four equivalents of piperidine
resulted in the desired formation of 1 (Scheme 2). For a better
À
understanding of the interactions between the Si O unit and
zinc, we examined the reactivity of the potential metal-
directing[15] disiloxane 1 towards zinc salts. Zinc(II) bromide
and zinc(II) acetate were chosen as two of the simplest
representatives.
Astonishingly, the treatment of 1 with two equivalents of
zinc(II) bromide or four equivalents of zinc(II) acetate in the
presence of water and under ambient atmosphere resulted in
the selective cleavage of the strong and unreactive Si-O-Si
[*] C. Dꢀschlein, J. O. Bauer, Prof. Dr. C. Strohmann
Anorganische Chemie, Technische Universitꢀt Dortmund
Otto-Hahn-Strasse 6, 44227 Dortmund (Germany)
Fax: (+49)231-755-7062
E-mail: mail@carsten-strohmann.de
[**] We are grateful to the Deutsche Forschungsgemeinschaft for
financial support. C.D. thanks the Studienstiftung des deutschen
Volkes for a doctoral scholarship, and J.O.B. thanks the Max Weber
Programm for an undergraduate scholarship.
Supporting information for this article, including experimental
details [synthesis of all compounds including all analytical data
(liquid and solid state NMR, MS, CHN, MP, X-Ray)], is available on
the WWW under http://dx.doi.org/10.1002/anie.200902318.
Scheme 2. Synthesis of 1 and selective Si-O-Si bond cleavage with
ZnBr2 and Zn(OAc)2 to form the water-stable silanolates 3 and 4.[16]
8074
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2009, 48, 8074 –8077

Angewandte
Chemie
À
bond to form quantitatively the two uncommon crystalline
solids 3 and 4 (Scheme 2 and Figure 1).
Si O units, thus leading to a positive charge located at the
amino function counterbalanced by a negative charge located
at the oxygen atom. Thus, there is no hint of the expected
silanol-like structure (Si-OH-Zn; A in Scheme 1) as proposed
for molecular metal silanediols under aqueous conditions (e.g.
the thermolysin/silanediol complex).[11] Instead, heretofore
unknown silanolate complexes with central Si-O-Zn frag-
ments are formed that are highly stable in the presence of
water (B in Scheme 1). Quantum chemical calculations
[B3LYP/6-31 + G(d)][17] on the silanolate 3 (Si-O-Zn) and its
hypothetical silanol (Si-OH-Zn; hydrogen atom not bound to
nitrogen) further provided an energetic preference for 3 of
157 kJmolÀ1, thus confirming the experimental observation.
How can this uncommon stability be explained? The
central R2R’Si-O-ZnX2X’ units of 3 and 4 possess fourfold-
coordinated zinc atoms comparable to the pseudo-tetrahedral
coordination geometry of zinc in many of its coordination
Compound 3 crystallized from acetone/water in the
monoclinic space group P21/n as colorless needles, and 4
crystallized from acetone/acetonitrile/water in the monoclinic
space group P21/c as colorless plates.[16] Compound 3 forms a
compounds.[10,18] All O Zn bond lengths are comparable, with
À
À
À
1.981(4) ꢀ (O Zn) for 3 and 1.975(2) (O1 Zn1) and
À
1.955(3) ꢀ (O1 Zn2) for 4. These distances are significantly
longer than the sum of the covalent radii of oxygen and zinc
(1.89 ꢀ), but they are in the same range as the zinc–oxygen
distances in various, mostly ionic, zinc silicates such as
willemite (mean value 1.98 ꢀ).[19] Consequently, the high
stability of 3 and 4 under aqueous conditions can be under-
stood by charge separation between the positively charged
nitrogen atom and the negatively charged oxygen atom. It is
well known that zwitterionic species strongly stabilize molec-
ular structures, for example, in many biological systems (such
as amino acids).[20] Analogously, the intramolecular zwitter-
ionic effect present in 3 and 4 enables their synthesis and
causes their extraordinary high stability in the presence of
water.
Nevertheless, the following central question emerged:
Are the shown structures of 3 and 4 maintained in solution?
To answer this decisive question, we performed detailed
NMR spectroscopic studies in solution and the solid state (all
spectra are shown in the Supporting Information). In both
cases, only one defined compound could be identified in
solution, thus underlining the homogeneity of the bulk
material, not only in the crystal (the homogeneity of the
crystalline material was further confirmed by powder X-ray
diffraction analysis). The 29Si NMR spectra of 3 and 4 in
solution showed one resonance signal each at d = 4.7 (3) and
6.3 ppm (4); these chemical shifts are in the same range as
those in the solid-state spectra. NMR spectroscopic quantum
chemical calculations [GAIO/B3LYP/IGLO-II//B3LYP/6-
31 + G(d)][17] on 3 and 4 confirmed the chemical shifts of
the 29Si signals in this range. Only one resonance was
identified for 3 (d = 3.7 ppm) in the solid state, whereas two
signals were located for 4 (d = 6.6 and 6.9 ppm). This
observation is in agreement with the X-ray structural analysis
of 4, which possesses two molecules in the asymmetric unit,
which results in two signals (the same is true for the 13C and
15N signals). The 13C signals of both molecules have compa-
rable values in the solid state and in solution. It is noteworthy
that the 13C signals of the piperidinomethyl groups are shifted
downfield compared to the reactant 1, which is a clear
indication of protonated nitrogen atoms. A further interesting
Figure 1. Molecular structures of 3 (top) and 4 (bottom, one of two
molecules in the asymmetric unit). Selected bond lengths [ꢁ]: 3: Br1–
Zn 2.3950(11), Br2–Zn 2.3359(10), O–Si 1.621(4), O–Zn 1.981(4), O–
Zn’ 1.983(4), Zn–O’ 1.983(4), symmetry transformation ’: Àx, Ày+1,
Àz+2; 4: O1–Si1 1.626(3), O1–Zn2 1.955(3), O1–Zn1 1.975(2), O3–
Zn2 1.971(3), O5–Zn2 1.959(3), O6–Zn1 2.001(3), O7–Zn2 1.976(3),
O8–Zn2 1.921(3).
dimeric structure with an inversion center located in the
middle of its Zn-O-Zn’-O’ ring. The asymmetric unit of 4
contains two molecules. In comparison to 3, only one R2R’SiO
unit is present in 4 with two zinc atoms coordinated to the
oxygen atom at silicon. To complete its coordination sphere,
each zinc atom is coordinated by three additional oxygen
atoms of the acetate groups; two acetate units bridge both
zinc atoms. Consequently, the successful isolation of these
structures demonstrates the following two facts: 1) Contrary
to previous opinion, molecular metallasilanolates are obvi-
ously stable under aqueous conditions. 2) Zinc compounds
À
are able to cleave Si O bonds. Below, the uncommon
structures of 3 and 4 will be discussed in detail, with special
focus on their high stability in the presence of water.
Afterwards, we will take a closer look at the bond cleavage
process.
In the in the X-ray diffraction analyses of 3 and 4,
hydrogen atoms were found and freely refined at the nitrogen
atoms in both molecules and not at the oxygen atoms of the
Angew. Chem. Int. Ed. 2009, 48, 8074 –8077
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
8075

Communications
detail in the 1H NMR spectra is that the NCH2CH2CH2 (in 3)
results in the formation of the experimentally observed Si-O-
Zn unit of the zinc silanolate. This transition state showed a
barrier of 103 kJmolÀ1, which can be overcome at room
temperature. Unconsidered proton-transfer processes, which
easily proceed under aqueous conditions, should further
stabilize the produced formal silyl cation, thus resulting in a
significant decrease of the energy barrier of these gas-phase
calculations.
The presented formation of water-stable molecular zinc
silanolates by selective Si-O-Si bond cleavage in amino-
methyl-functionalized disiloxanes with zinc(II) salts is a
remarkable reaction for the understanding of siloxane
chemistry. Not only are these hydrolysis-resistant metallasi-
lanolates of transition metals the first molecular systems of
their kind, but the reaction also demonstrates a simple way to
cleave the strong Si-O-Si bond under mild conditions. The
understanding of this basic process is further of special
interest in materials science for artificial surface design as well
as in many chemical processes, including silanes in the
presence of water and amines. Moreover, the presented
reaction suggests a starting point for a better chemical
understanding of, for example, biological processes in
nature, including siloxanes and metal-containing com-
pounds.[22] At the moment we are varying amino ligands,
substituents at silicon, and the metal salt to gain a deeper
understanding of this reaction.
and NCH2CH2CH2 and NCH2CH2CH2 (in 4) groups each give
different resonance signals, thus indicating the complexation
of the zinc salt to the silicon fragment. Further NMR
spectroscopic measurements of 3 and 4 in the presence of
the free disiloxane 1 showed only the appearance of the
resonance signals of the disiloxane, whereas the addition of
the particular zinc salt had no effect on the spectra. Thus, the
split proton resonance signals of 3 and 4 can only be attributed
to the coordination of the zinc salt and not to the existence of
additional compounds in solution (e.g. a hydrobromide or
hydroacetate). Consequently, the NMR spectroscopy studies
indicate that 3 and 4 have the same structures in solution as in
the solid state.
For a better understanding of the ongoing processes of the
presented reaction, one decisive question remains: How can
the mechanism for the cleavage of the Si-O-Si bond in 1 and
the formation of 3 and 4 be understood? To get a deeper
insight, we performed DFT calculations[17] for a zinc-assisted
hydrolysis of the model system (H2NCH2)SiH2OSiH3 (C,
smaller model for 3) via a pentacoordinated transition state
(Figure 2). ZnBr2(H2O)2 (D) was chosen as a possible starting
compound for the zinc salt under aqueous conditions.
In the first step of the bond cleavage, the zinc compound
D is coordinated by the aminomethyl sidearm of the
disiloxane C under abstraction of one molecule of water.
Additionally, the coordination of the oxygen atom of the Si-
O-Si unit to the zinc center results in the approach of the
reactive groups forming the starting system E of the
subsequent cleavage reaction. The formation of E is favored
by 40 kJmolÀ1 compared to the uncoordinated starting
molecules and thus should readily proceed at room temper-
ature.
Received: April 30, 2009
Revised: July 10, 2009
Published online: September 24, 2009
Keywords: metal complexes · metallasilanolates · silicon · zinc ·
.
zwitterions
Further approach of the remaining water molecule to the
silicon center of the model system E results in the formation
of the pentacoordinated transition state TS with the leaving
[1] Examples can be found in all commonly used chemistry text-
books. Because of this high stability and low reactivity, silicones
have a variety of applications, for example, as insulating
compounds, as silicone polymers, as greases, or even as flexible
catheters in medicine.
O(ZnBr2) SiR3 group arranged in axial position.[21] The
À
À
elongation of the Si O bond and its subsequent cleavage
[2] For example, see: R. Murugavel, A. Voigt, M. G.
Walawalkar, H. W. Roesky, Chem. Rev. 1996, 96,
2205 – 2236.
[3] For two examples, see: a) F. Baud-Grasset, J.-C.
Palla, DE69627324T2 11.12.2003, 2003; b) M. Oka-
moto, K. Miyazaki, A. Kado, E. Suzuki, Chem.
Commun. 2001, 1838 – 1839.
[4] a) F. J. Feher, T. A. Budzichowski, Polyhedron 1995,
14, 3239 – 3253; b) V. Lorenz, A. Fischer, S. Giess-
mann, J. W. Gilje, Y. Gunꢁko, K. Jacob, F. T.
Edelmann, Coord. Chem. Rev. 2000, 206–207,
321 – 368; c) J. Beckmann, K. Jurkschat, Coord.
Chem. Rev. 2001, 215, 267 – 300.
[5] For selected examples on, for example, stannoxanes,
see: a) J. Beckmann, M. Bieseman, K. Hassler, K.
Jurkschat, J. C. Martins, M. Schꢂrmann, R. Willem,
Inorg. Chem. 1998, 37, 4891 – 4897; b) M. Schulte,
M. Schꢂrmann, D. Dakternieks, K. Jurkschat,
Chem. Commun. 1999, 1291 – 1292; c) J. Beckmann,
K. Jurkschat, M. Schꢂrmann, Organometallics 2001,
Figure 2. Coordination of the disiloxane (H2NCH2)H2SiOSiH3 (C) to ZnBr2(H2O)2
(D) forming the starting compound E of the subsequent metallasilanolate building
(left); transition state TS for the metallasilanolate formation (right).
20, 5125 – 5133.
[6] For some examples and applications, see: a) H. W.
Roesky, G. Anantharaman, V. Chandrasekhar, V.
8076 www.angewandte.org
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2009, 48, 8074 –8077

Angewandte
Chemie
Jancik, S. Singh, Chem. Eur. J. 2004, 10, 4106 – 4114; b) D. E.
Leyden, G. H. Luttrell, A. E. Sloan, N. J. De Angelis, Anal.
Chim. Acta 1976, 84, 97 – 108; c) H. C. L. Abbenhuis, Chem. Eur.
J. 2000, 6, 25 – 32; d) R. W. J. M. Hanssen, R. A. Van Santen,
H. C. L. Abbenhuis, Eur. J. Inorg. Chem. 2004, 675 – 683.
[7] For examples concerning siloxanes with transition metals, see: F.
Schindler, H. Schmidbaur, Angew. Chem. 1967, 79, 697 – 708;
Angew. Chem. Int. Ed. Engl. 1967, 6, 683 – 694.
[8] For examples concerning siloxanes with main-group metals, see:
H. Schmidbaur, Angew. Chem. 1965, 77, 206 – 216; Angew.
Chem. Int. Ed. Engl. 1965, 4, 201 – 211.
[9] For examples concerning lithiosilanolates, see: a) H.-W. Lerner,
S. Scholz, N. Wiberg, K. Polborn, M. Bolte, M. Wagner, Z.
Anorg. Allg. Chem. 2005, 631, 1863 – 1870; b) B. Kern, H. Vitze,
M. Bolte, M. Wagner, H.-W. Lerner, Z. Anorg. Allg. Chem. 2008,
634, 1830 – 1832.
128, 704 – 705; b) C. Dꢃschlein, C. Strohmann, Eur. J. Inorg.
Chem. 2009, 43 – 52; c) C. Strohmann, C. Dꢃschlein, Chem.
Commun. 2008, 2791 – 2793; d) C. Strohmann, O. Ulbrich, D.
Auer, Eur. J. Inorg. Chem. 2001, 1013 – 1018.
[15] For some overview articles concerning the precoordination of
metals by amino side arms, see: a) V. H. Gessner, C. Dꢃschlein,
C. Strohmann, Chem. Eur. J. 2009, 15, 3320 – 3334; b) C. M.
Whisler, S. MacNeil, V. Snieckus, P. Beak, Angew. Chem. 2004,
116, 2256 – 2276; Angew. Chem. Int. Ed. 2004, 43, 2206 – 2225;
c) P. Beak, A. I. Meyers, Acc. Chem. Res. 1986, 19, 356 – 363.
[16] The use of the organic solvents (acetone and acetonitrile) is only
necessary for better crystallization.
[17] Gaussian 03 (Revision E.01): Frisch et al., for details see the
Supporting Information.
[18] For some examples concerning coordination compounds of zinc
(fourfold-, fivefold-, and sixfold-coordinated zinc), see: a) F.
Meyer, Eur. J. Inorg. Chem. 2006, 3789 – 3800; b) B. Bauer-
Siebenlist, S. Dechert, F. Meyer, Chem. Eur. J. 2005, 11, 5343 –
5352; c) B. Bauer-Siebenlist, F. Meyer, E. Farkas, D. Vidovic, S.
Dechert, Chem. Eur. J. 2005, 11, 4349 – 4360.
[10] For a good overview of the role of zinc in enzymes, see: G.
Parkin, Chem. Rev. 2004, 104, 699 – 767.
[11] D. H. Juers, J. Kim, B. W. Matthews, S. M. Sieburth, Biochem-
istry 2005, 44, 16524 – 16528.
[12] For a related example, see: G. Parkin, Chem. Commun. 2000,
1971 – 1985.
[19] N. N. Greenwood, A. Earnshaw, Chemistry of the elements, 1st
ed., Pergamon, Oxford (UK), 1984.
[13] For some examples of our aminomethyl-functionalized silanes,
see: a) C. Strohmann, C. Dꢃschlein, M. Kellert, D. Auer, Angew.
Chem. 2007, 119, 4864 – 4866; Angew. Chem. Int. Ed. 2007, 46,
4780 – 4782; b) C. Dꢃschlein, V. H. Gessner, C. Strohmann, Acta
Crystallogr. Sect. E 2008, 64, o1950; c) C. Strohmann, C.
Dꢃschlein, Organometallics 2008, 27, 2499 – 2504; d) H. Ott, C.
Dꢃschlein, D. Leusser, D. Schildbach, T. Seibel, D. Stalke, C.
Strohmann, J. Am. Chem. Soc. 2008, 130, 11901 – 11911; e) C.
Strohmann, J. Hꢄrnig, D. Auer, Chem. Commun. 2002, 766 – 767;
f) C. Strohmann, M. Bindl, V. C. Vraaß, J. Hꢄrnig, Angew. Chem.
2004, 116, 1029 – 1032; Angew. Chem. Int. Ed. 2004, 43, 1011 –
1014.
[20] For one current of the countless examples, see: M. F. Bush, J.
Oomens, R. J. Saykally, E. R. Williams, J. Am. Chem. Soc. 2008,
130, 6463 – 6471.
[21] For a detailed discussion on the hydrolysis of silanes via
pentacoordinated species, see: I. H. Krouse, P. G. Wenthold,
Organometallics 2004, 23, 2573 – 2582.
[22] For possible future applications of the presented Si-O-Si
cleavage and metallasilanolate formation, see: a) M. Sumper,
E. Brunner, Adv. Funct. Mater. 2006, 16, 17 – 26; b) E. Bꢃuerlein,
Angew. Chem. 2003, 115, 636 – 664; Angew. Chem. Int. Ed. 2003,
42, 614 – 641; c) M. Sumper, Angew. Chem. 2004, 116, 2301 –
2304; Angew. Chem. Int. Ed. 2004, 43, 2251 – 2254; d) M.
Sumper, N. Krꢄger, J. Mater. Chem. 2004, 14, 2059 – 2065.
[14] For some examples of our amino-functionalized silanes, see:
a) C. Strohmann, C. Dꢃschlein, D. Auer, J. Am. Chem. Soc. 2006,
Angew. Chem. Int. Ed. 2009, 48, 8074 –8077
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org 8077