Ring-opening metathesis polymerization-derived, polymer-bound Cu-catalysts for click-chemistry and hydrosilylation reactions under micellar conditions

Article abstract of DOI:10.1039/b909180g

Ring-opening metathesis polymerization has been used for the synthesis of the amphiphilic block-copolymer poly(M1-co-M3)-b-poly(M2) from the hydrophilic monomer 5-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxymethyl}-7-oxabicyclo[2.2.1] hept-2-ene (M2), and the

Full text of DOI:10.1039/b909180g

View Article Online / Journal Homepage / Table of Contents for this issue
This paper is published as part of a Dalton Transactions themed issue on:
Metal-catalysed Polymerisation
Guest Editors: Barbara Milani and Carmen Claver
University of Trieste, Italy and Universitat Rovira i Virgili, Tarragona, Spain
Published in issue 41, 2009 of Dalton Transactions
Image reproduced with permission of Eugene Chen
Articles published in this issue include:
PERSPECTIVES:
New application for metallocene catalysts in olefin polymerization
Walter Kaminsky, Andreas Funck and Heinrich Hähnsen,
Dalton Trans., 2009, DOI: 10.1039/B910542P
Metal-catalysed olefin polymerisation into the new millennium: a perspective outlook
Vincenzo Busico, Dalton Trans., 2009, DOI: 10.1039/B911862B
HOT PAPERS:
Activation of a bis(phenoxy-amine) precatalyst for olefin polymerisation: first evidence for an outer
sphere ion pair with the methylborate counterion
Gianluca Ciancaleoni, Natascia Fraldi, Peter H. M. Budzelaar, Vincenzo Busico and Alceo
Macchioni, Dalton Trans., 2009, DOI: 10.1039/B908805A
Palladium(II)-catalyzed copolymerization of styrenes with carbon monoxide: mechanism of chain
propagation and chain transfer
Francis C. Rix, Michael J. Rachita, Mark I. Wagner, Maurice Brookhart, Barbara Milani and James
C. Barborak, Dalton Trans., 2009, DOI: 10.1039/B911392D
Visit the Dalton Transactions website for more cutting-edge organometallic and catalysis research
www.rsc.org/dalton

PAPER
www.rsc.org/dalton | Dalton Transactions
Ring-opening metathesis polymerization-derived, polymer-bound Cu-catalysts
for click-chemistry and hydrosilylation reactions under micellar conditions†
Gajanan M. Pawar,a Bhasker Bantu,a Jochen Weckesser,b Siegfried Blechert,*b Klaus Wurstd and
Michael R. Buchmeiser*a,c
Received 11th May 2009, Accepted 26th June 2009
First published as an Advance Article on the web 31st July 2009
DOI: 10.1039/b909180g
Ring-opening metathesis polymerization has been used for the synthesis of the amphiphilic
block-copolymer poly(M1-co-M3)-b-poly(M2) from the hydrophilic monomer
5-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxymethyl}-7-oxabicyclo[2.2.1]hept-2-ene (M2), and the
hydrophobic monomers endo,exo-5-decyloxymethyl-bicyclo[2.2.1]hept-2-ene (M1) and 1,3-di(1-
mesityl)-4-{[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)oxy]methyl}-4,5-dihydro-1H-imidazol-3-ium
carboxylate (M3). Poly(M1-co-M3)-b-poly(M2) was loaded with Cu and the resulting CuI-loaded
polymer poly(M1-co-M3)-b-poly(M2)–Cu was used for a series of Cu-catalyzed reactions under
micellar conditions, i.e. for the [3 + 2] cycloaddition of azides to alkynes and for carbonyl
hydrosilylation reactions. Under such micellar conditions, the polymer-bound Cu-catalyst was found to
be an efficient catalyst for all reactions investigated. Turn-over numbers (TONs) in cycloaddition
reactions were in the range of 200–375, those in hydrosilylation reactions ~2000 allowing for
Cu-loadings of 0.05 mol% with respect to substrate.
(ROMP) of the norborn-2-ene-based hydrophilic monomer 5-{2-
[2-(2-methoxy-ethoxy)-ethoxy]-ethoxymethyl}-7-oxabicyclo-
[2.2.1]hept-2-ene (M2), and the hydrophobic monomers endo,exo-
5-decyloxymethyl-bicyclo[2.2.1]hept-2-ene (M1) and 1,3-di(1-
mesityl)-4-{[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)oxy]methyl}-
4,5-dihydro-1H-imidazol-3-ium carboxylate (M3). Heating of the
amphiphilic block copolymer poly(M1-co-M3)-b-poly(M2) in the
presence of a soluble Cu(I) salt resulted in the release of CO2 and
immobilization of the Cu(I) via Cu–NHC complex formation. This
polymer-bound Cu-catalyst was used under micellar conditions
in the [3 + 2] cycloaddition of azides to alkynes and in the
hydrosilylation of carbonyl compounds.
Introduction
Amphiphilic block copolymers1–5 have achieved wide attention,
e.g., in the area of micellar catalysis6–11 where, most recently,
catalysts bound to amphiphilic block copolymers have become
an important research topic due to the stability of these systems in
aqueous media and the ease of product–catalyst separation.12–16
Such amphiphilic polymer-bound catalysts fulfil two require-
ments: on the one hand, they combine the advantages of both ho-
mogeneous and heterogeneous catalysts in one system,17–22 and on
the other hand, the catalyst can be permanently linked to the block
copolymer, which substantially reduces metal leaching and allows
for the separation/reuse of the catalyst. In case reactions are run
in polar media, the catalyst is best located inside the hydrophobic
micellar core, where, upon micelle formation of the functionalized
block copolymer, the monomer will also accumulate. This leads to
high educt concentrations at the polymer-bound catalyst, leading
to remarkable catalytic activity in water.23–25 Here, we demonstrate
a synthetic protocol for the immobilization26–39 of copper(I) to an
amphiphilic block copolymer based on a protected N-heterocyclic
carbene (NHC) bearing ligand.40–44 The amphiphilic block copoly-
mer was prepared via ring-opening metathesis polymerization
Results and discussion
Syntheses of monomers
The syntheses of the norborn-2-ene-based monomers M1, M2
and M3 are outlined in Scheme 1. M1 was synthesized by the
reaction of 5-norbornenyl-2-methanol with decylbromide in 63%
yield. Hydrophilic M2 was synthesized from 7-oxanorborn-5-
ene-2-methanol and toluene-4-sulfonic acid 2-[2-(2-methoxy-
ethoxy]-ethyl ester in 41% yield. The use of a 7-oxanorborn-2-ene
instead of a norborn-2-ene additionally enhances the hydrophilic
character of the monomer. M3 was accessible in 85% yield
by the reaction of 1,3-di(1-mesityl)-4-{[(bicyclo[2.2.1]hept-
5-en-2-ylcarbonyl)oxy]methyl}-4,5-dihydro-1H-imidazol 3-ium
tetrafluoroborate with KH, followed by the reaction with
dry CO2.
aLeibniz-Institut fu¨r Oberfla¨chenmodifizierung e.V., Permoserstraße 15,
D-04318 Leipzig, Germany. E-mail: michael.buchmeiser@iom-leipzig.de
bInstitut fu¨r Chemie, Technische Universita¨t Berlin, Straße des 17 Juni 135,
D-10623 Berlin. E-mail: blechert@chemie.tu-berlin.de
cInstitut fu¨r Technische Chemie, Universita¨t Leipzig, Linne´straße 3, D-04103
Leipzig, Germany
dInstitut fu¨r Allgemeine, Anorganische und Theoretische Chemie, Universita¨t
Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
Homopolymerization and block copolymerization
† Electronic supplementary information (ESI) available: Analytical spectra
and crystal data and structure refinement for 1. CCDC reference number
731614. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/b909180g
In order to gain information on the polymerization propensity
of M1, M2 and M3 with the 3rd generation Grubbs initiator
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 9043–9051 | 9043
©

Scheme 1 Syntheses of M1, M2 and M3.
RuCl2(Py)2(IMesH2)(CHPh), the corresponding homopolymer-
Synthesis of the amphiphilic block copolymer poly(M1-co-M3)-
b-poly(M2), cmc measurements and catalyst formation
izations were carried out in CHCl3 at room temperature. The
homopolymers poly(M1), poly(M2) and poly(M3) were isolated in
75–85% yield and displayed excellent solubility in CHCl3, CH2Cl2
and THF. In addition, the polymerization kinetics of M1 could be
determined (Fig. S1, ESI†). As can be seen, the polymerization of
M1 followed 1st order kinetics, suggesting a living polymerization
setup and quantitative initiation. This is additionally supported by
the good agreement between the theoretical and experimentally
determined molecular weights (Mn) and the low polydispersity
index (PDI). Thus, the values for Mn and the PDI observed for
poly(M1) were Mn = 9600 g mol-1, PDI = 1.16 (Mn(calc) = 10 700 g
mol-1), those for poly(M2) and poly(M3) Mn = 12 600 g mol-1,
PDI = 1.19 (Mn(calc) = 13 600 g mol-1) and Mn = 80 400 g mol-1,
PDI = 1.01 (Mn(calc) = 50 000 g mol-1), respectively. It is worth
noting that the molecular weights of poly(M1) and poly(M2) were
measured by gel permeation chromatography (GPC) in THF, while
those of poly(M3) were measured in DMF.
The amphiphilic block-copolymer was synthesized from hy-
drophilic M2 and the hydrophobic monomers M1 and M3 by
the action of RuCl2(Py)2(IMesH2)(CHPh) in CHCl3 at room
temperature (Scheme 2). In the first step, monomers M1 and
M3 were randomly copolymerized, then, a small sample was
withdrawn from the reaction mixture for GPC measurements. As
can be deduced from Table 1, the theoretical and experimentally
determined degrees of (co)polymerization for M1 and M3 were in
good agreement. Finally, M2 was added, resulting in a well-defined
block copolymer with Mn = 26 400 g mol-1 (PDI = 1.41) in 73%
isolated yield. Only a very minor signal for the homopolymer
poly-M2 was observed (Fig. S2, ESI†). From 1H-NMR (Fig. S3,
ESI†) and the GPC data of poly(M1-co-M3) and poly(M1-co-
M3)-b-poly(M2), we could determine the actual incorporation of
monomers M1–M3 into the final block copolymer and the actual
Scheme 2 Synthesis of poly(M1-co-M3)-b-poly(M2).
This journal is
9044 | Dalton Trans., 2009, 9043–9051
The Royal Society of Chemistry 2009
©

Table 1 GPC data for poly(M1-co-M3)-b-poly(M2)a
DPb (calcd)
DP (found)
Blocks
M
n(calc)/g mol-1
M
n(found)/g mol-1
PDI
M1
M3
M2
M1
M3
M2
poly(M1-co-M3)-
poly(M1-co-M3)-b-poly(M2)
9100
30 900
10 800
26 400
1.20
1.41
30
30
5
5
—
80
27
27
7
7
—
57
a In THF versus polystyrene standards. b DP = degree of polymerization.
block sizes, which were in good agreement with the theoretical
ones. Data are summarized in Table 1.
on the reaction conditions47 as evidenced by the reaction of the
CO2-protected NHC 1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-
ium carboxylate49 in the absence of any base with CuCl in
toluene at 100 ◦C (Scheme 4). In contrast to the base-catalyzed
reaction,45 we selectively obtained the mono-NHC–Cu complex
[Cu(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)Cl] (1) in
95% yield. Its structure is shown in Fig. 1.
Since the poly(M2) block in the amphiphilic block copolymer is
soluble in both water and DMF while the poly(M1-co-M3) block is
not, micelles form in water as well as in DMF once the critical mi-
celle forming concentration (cmc) is reached. The cmc of poly(M1-
co-M3)-b-poly(M2) was determined by fluorescence spectroscopy
(Fig. S4–S7, ESI for fluorescence spectra†). For measurements in
water and DMF, 6-p-toluidene-2-naphthylsufonic acid (10-6 and
10-4 mol L-1) was used as a fluorescence probe and the cmcs were
determined as follows: cmcwater = 1.5 ¥ 10-4 mol L-1; cmcDMF
=
1.7 ¥ 10-4 mol L-1.
The polymer-bound Cu-catalyst poly(M1-co-M3)-b-poly(M2)–
Cu was synthesized by the reaction of copper(I) chloride with the
CO2-protected NHC-based poly(M1-co-M3)-b-poly(M2) in 93%
yield (Scheme 3). The Cu content was determined by inductively
coupled plasma optical emission spectrometry (ICP-OES) after
dissolving a 10.5 mg sample in aqua regia and found to be
6.9 mg g-1 (0.11 mmol g-1) polymer. In view of the amount of
NHC present in the polymer (0.267 mmol g-1), this corresponds to
a Cu-loading of 41%. The presence of imidazolium moieties is also
Scheme 4 Synthesis of 1.
1
clearly visible in the H-NMR (d = 8.4 ppm). Integration versus
the CH3 groups of the decyloxy group (d = 0.8 ppm) confirms a
Cu-loading of ca. 40% as determined by ICP-OES (Fig. S8, ESI†).
Synthesis of a model catalyst
CuCl(1,3-dimesityltetrahydropyrimini-2-ylidene) (1)
Fig. 1 X-Ray structure of 1.
Cu(I) is known to be capable of forming complexes of the
+
-
general formula [Cu(NHC)2 CuCl2 ] where the complex is made
from the corresponding imidazolium or pyridinium salts in the
presence of a strong base.45,46 However, the structure of the block
copolymer would hardly allow for the formation of such com-
plexes, since the NHC moieties would be too far away from each
other. In addition, the structure of a metal–NHC complex, here
Compound 1 crystallizes in the orthorhombic space group
Pbcn with a = 3046.27(5) pm, b = 890.30(2) pm, c =
1587.30(3) pm , a = b = g = 90◦, Z = 8. The Cu–NHC distance
(Cu(1)–C(1)) distance was 189.2(3) nm and is thus very similar to
the one found in CuCl(1,3-di(2-Pr)-3,4,5,6-tetrahydropyrimidin-
ylidene).45 The distance Cu(1)–Cl(1) was found to be
210.11(9) nm, again virtually identical to the one found in
+
-
[Cu(NHC)2 CuCl2 ] versus [Cu(NHC)Cl], depends very much
Scheme 3 Synthesis of polymer-bound Cu-catalyst of poly(M1-co-M3)-b-poly(M2)–Cu.
The Royal Society of Chemistry 2009 Dalton Trans., 2009, 9043–9051 | 9045
This journal is
©

CuCl(1,3-di(2-Pr)-3,4,5,6-tetrahydropyrimidin-ylidene).45 As ex-
pected, the Cl-ligand was arranged in an almost perfect trans-
position to the NHC, resulting in a C(1)–Cu(1)–Cl(1) angle of
176.20(9)◦. Based on these findings, we also attribute a mono-
NHC–Cu structure to the polymer-bound catalyst (Scheme 3).
Table 2 Results of the [3 + 2] cycloaddition of azides and alkynes
catalyzed by catalyzed by poly(M1-co-M3)-b-poly(M2)–Cua
Entry Triazole
Time/h Yield (%)b
TON
265
1
16
53
Cu-catalyzed [3 + 2] cycloaddition of azides to alkynes
(click-chemistry)50
Poly(M1-co-M3)-b-poly(M2)–Cu was used in the Cu(I) catalyzed
[3 + 2] cycloaddition of organic azides to alkynes51 under micellar
conditions (Scheme 5). A variety of organic azides and alkynes
were used. In water, poly(M1-co-M3)-b-poly(M2)–Cu showed
excellent reactivity allowing for the synthesis of the corresponding
1,4-disubstituted 1,2,3-triazoles. In order to determine the maxi-
mum turn over numbers (TONs), reactions were run at a 0.2 mol%
level of Cu, resulting in yields between 40 and 75% and TONs(max)
in the range of 200–375 (Table 2). All 1,2,3-triazoles were isolated
with high purity after simple filtration or extraction. The copper
leaching to the products was determined by means of ICP-OES
and was found to be <50 ppm, which translates into a Cu-leaching
of <3%.
2
3
16
46
230
200
16
40
4
5
18
18
58
65
290
325
Scheme 5 [3 + 2] Cycloaddition of azides and alkynes catalyzed by
poly(M1-co-M3)-b-poly(M2)–Cu.
Recycling studies
In order to retrieve some information on the stability of the
polymer-bound Cu-catalyst poly(M1-co-M3)-b-poly(M2)–Cu, we
performed recycling studies. For this purpose, a defined amount
of poly(M1-co-M3)-b-poly(M2)–Cu was used in the coupling
reaction of phenyacetylene with 3-methylbenzylazide at room
temperature. Once the reaction was complete, the product was
extracted from the aqueous solution with diethyl ether and
poly(M1-co-M3)-b-poly(M2)–Cu was reused. Using poly(M1-co-
M3)-b-poly(M2)–Cu on a 1 mol% base with respect to the azide,
conversions of 100, 100, 100 and 95% were observed within 4
consecutive runs, thus illustrating the good recyclability of the
micellar catalyst.
6
18
46
230
7
8
14
14
75
70
375
350
Hydrosilylation of carbonyl compounds52
Cu–NHC complexes are known to catalyze the hydrosilylation of
carbonyl compounds (Scheme 6).45,46,48 This reaction represents a
direct route to protected alcohols and is a useful synthetic alterna-
tive to the reduction of carbonyl groups. Here, the hydrosilylation
of various carbonyl compounds including aromatic aldehydes
and ketones was carried out under micellar conditions in DMF
using poly(M1-co-M3)-b-poly(M2)–Cu. Product quantification
a 0.2 mol% of Cu with respect to the azide was used. Reactions were run
in water at room temperature. b Isolated yields.
Scheme
6
Hydrosilylation of carbonyl compounds catalyzed by
poly(M1-co-M3)-b-poly(M2)–Cu.
9046 | Dalton Trans., 2009, 9043–9051
This journal is
The Royal Society of Chemistry 2009
©

Table 3 Hydrosilylation of carbonyl compounds with triethylsilane catalyzed by poly(M1-co-M3)-b-poly(M2)–Cu
Educt/product
Reaction time/min
Yield (%)b TON TOF (h-1)
1
2
3
4
5
4-Chlorobenzaldehyde/4-Cl-phenyl-1-triethoxysilylmethane
Benzophenone/diphenyltriethoxymethane
Benzaldehyde/phenyltriethoxysilylmethane
4-N,N-Dimethylaminobenzaldehyde/4-N,N-dimethylaminophenyltriethoxysilylmethane 30
4-Fluorobenzaldehyde/4-F-phenyltriethoxysilylmethane 60
30
30
30
100
100
100
100
95
2000 4000
2000 4000
2000 4000
2000 4000
1900 1900
a 0.05 mol% of Cu and 15 mol% of potassium tert-butoxide with respect to the carbonyl compound were used. Reactions were run in DMF at 60 ◦C.
b Determined by GC-MS.
was accomplished by GC-MS using tert-butylbenzene as an
internal standard. It is worth mentioning that, while the reaction
in water produced a mixture of the O–SiEt3-protected alcohols,
the free alcohols and the corresponding carboxylic acid, the
reaction under micellar conditions in DMF allowed for the
selective synthesis of the corresponding O–SiEt3-protected species.
A summary of the results is given in Table 3. As can be seen,
the catalyst showed excellent reactivity in these reactions. Thus,
using a catalyst loading of 0.05 mol% of Cu with respect to
the corresponding carbonyl compound, TONs up to 2000 and
turn-over frequencies (TOFs) up to 4000 h-1 were achieved. Yields
were in the 90–100% range within 30 min (60 min for 4-F-phenyl-
triethoxysilylmethane).
(MTBE) was used as received (Acros Organics, Geel, Belgium).
NMR spectra were recorded at room temperature on a Bruker AM
400 (400 MHz for proton and 100.6 MHz for carbon), a Bruker
Avance 600 (600.25 MHz for proton and 150.93 MHz for carbon)
and a Bruker Avance 250 (250.13 MHz for proton and 62.90 MHz
for carbon) spectrometer, respectively. Proton and carbon NMR
spectra were referenced to the internal solvent resonance and
are reported in ppm relative to tetramethylsilane. Deuterated
NMR solvents d6-benzene and d8-THF were dried and dis-
tilled from sodium/benzophenone ketyl, d2-dichloromethane and
d3-chloroform were dried and distilled from calcium hydride.
Molecular weights and polydispersity indices (PDIs) of the poly-
mers were determined by GPC at 30 ◦C on Polymer Laboratories
columns (PLgel 10 mm MIXED-B, 7.5 ¥ 300 mm) in THF using
a Waters Autosampler, a Waters 484 UV detector (254 nm),
a light scattering detector (Wyatt, USA) and an Optilab Rex
refractive index detector (685 nm, Wyatt). The flow rate was
set to 0.7 mL min-1. Fluorescence testing was performed using
a Perkin-Elmer luminescence spectrometer LS50B. IR spectra
were recorded on a Bruker Vector 22 using ATR technology.
MS and HRMS were recorded on a Finnigan MAT 95 SQ or
Varian MAT 771. Ionization was achieved by electron impact (EI)
ionization applying an ionization potential of 70 eV unless noted
otherwise. The intensities of the fragments are reported in percent
relative to the strongest signal. Elemental analysis was carried out
on an Elementar Varia El (Analytik Jena). RuCl2(Py)2(IMesH2)-
(CHPh)53 and 1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ium
carboxylate49 were synthesized according to the literature.
Conclusion
In conclusion, the amphiphilic block copolymer poly(M1-co-
M3)-b-poly(M2) has been successfully synthesized via ring-
opening metathesis polymerization (ROMP) of norborn-2-ene and
7-oxanornorn-2-ene based hydrophilic (M2) and hydrophobic
(M1 and M3) monomers. The block copolymer forms micelles
in water and DMF with critical micellar concentrations (cmcs)
of 1.5 ¥ 10-4 mol L-1 and 1.7 ¥ 10-4 mol L-1, respectively, as
determined by fluorescence spectroscopy. An amphiphilic block
copolymer bound Cu-catalyst was synthesized by immobilization
of copper(I) to poly(M1-co-M3)-b-poly(M2). The polymer bound
Cu-catalyst was found to be an efficient catalyst in the Huisgen [3 +
2] cycloaddition of organic azides to alkynes allowing for TONs of
200–375 at room temperature. The polymer-bound catalyst may
be used consecutively and may easily be removed by filtration, thus
offering straight-forward access to cycloaddition products with a
low Cu-content (typically <50 ppm). Additionally, the polymer
bound Cu-catalyst was used in the hydrosilylation reactions of
carbonyl compounds, allowing for TONs of up to 2000 and high
TOFs of up to 4000 h-1.
endo,exo-5-Decyloxymethyl-bicyclo[2.2.1]hept-2-ene (M1)
5-Norbornene-2-methanol (6.0 g, 48.3 mmol) was added dropwise
at room temperature to a suspension of NaH (2.09 g, 87 mmol,
1.8 eq.) in 150 mL of absolute THF and the mixture were heated
to reflux for 18 h to afford a light brown solution. The mixture
was cooled to room temperature and decylbromide (11.1 mL,
53.1 mmol, 1.2 eq.) was added dropwise over a period of 15 min.
Tetrabutyl ammonium iodide (TBAI) (1.79 g, 1.6 mmol, 10 mol%)
was added and the mixture was heated under reflux for 8 h. The
reaction was monitored by TLC (eluent: hexanes : MTBE = 10 : 1,
Rf = 0.5). Once the reaction was completed, 90 mL of water
were added slowly at 0 ◦C and the organic layer was separated.
The aqueous layer was extracted with diethyl ether (3 ¥ 50 mL)
and the combined organic layers were washed with NaHCO3
(30 mL) and brine (30 mL), dried over MgSO4 and concentrated
in vacuo. The yellow residue was purified by flash chromatography
(SiO2, hexanes : MTBE = 50 : 1) to afford M1 (2.69 g, 63%) as a
Experimental
All manipulations were performed under a nitrogen atmosphere
in a glove box (MBraun LabMaster 130, MBraun, Garching,
Germany) or by standard Schlenk techniques unless stated other-
wise. Purchased starting materials were used without any further
purification. Pentane, diethyl ether, toluene, methylene chloride
and tetrahydrofuran (THF) were dried using a solvent purification
system (SPS, MBraun, Garching, Germany). Benzene, n-hexane
and dimethoxyethane (DME) were dried and distilled from
sodium/benzophenone ketyl under argon. tert-Butyl methyl ether
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 9043–9051 | 9047
©

-1
¯
colorless oil. FT-IR (ATR mode, cm ): n = 3059 (w), 2956 (s),
(m), 1316 (m), 1302 (m), 1249 (m), 1199 (m), 1106 (br), 919
(s), 903 (m), 853 (s), 710 (m); H-NMR (CDCl3, 400 MHz): d
1
1
2925 (s), 2854 (s), 1466 (m), 1112 (s), 719 (s); H-NMR (CDCl3,
=
400 MHz): d (ppm) = 0.49 (ddd, 1H, J = 11.6, 4.4 and 2.5 Hz,
(ppm) = 1.22 (dt, 1H, J = 11.5 and 4.1, CH CHCHCHexo),
=
=
CH CHCHCHendo), 0.88 (t, 3H, J = 6.9 Hz, C9H18CH3), 1.27
1.38 (dd, 1H, J = 11.5 and 8.0, CH CHCHCHendo), 1.83–
=
(m, 15H, 7 ¥ CH2CH2, CH CHCHCH2), 1.41 (dm, 1H, J =
1.90 (m, 1H, CHCH2O(CH2CH2O)3CH3), 3.36–3.41 (m, 1H,
CH2O(CH2CH2O)3CH3), 3.38 (s, 3H, OCH3), 3.50–3.56 (m,
3H, CH2O(CH2CH2O)3CH3, OCH2CH2O), 3.60–3.69 (m, 10H,
=
6.2 Hz, CH CHCHCH2), 1.56 (m, 2H, OCH2CH2), 1.81 (ddd,
=
1H, J = 13.1, 4.4 and 2.5 Hz, CH CHCHCHexo), 2.33 (m, 1H,
=
=
CHCH2OC10H21), 2.78 (br s, 1H, CH CHCH), 2.91 (br s, 1H,
5 ¥ OCH2CH2O), 4.86 (br s, 1H, CH CHCH), 4.93 (m, 1H,
CH CHCH), 3.00 (t, 1H, J = 9.2 Hz, CH2OC10H21), 3.13 (dd, 1H,
CH CHCH) and 6.30 (m, 2H, CH CH); 13C-NMR (CDCl3,
100 MHz): d (ppm) = 28.0 (t), 37.8 (d), 59.1 (q), 70.4, 70.5, 70.6,
70.6, 70.6, 72.0 and 73.8 (all CH2), 78.3, 79.7, 132.5 and 136.2 (all
CH); HR-MS calcd for C14H24O5: m/z = 273.1702, found m/z =
=
=
=
J = 9.2 and 6.6 Hz, CH2OC10H21), 3.28–3.47 (m, 2H, OCH2C9H19),
=
5.93 (dd, 1H, J = 5.7 and 2.9 Hz, CH CH) and 6.12 (dd, 1H,
J = 5.7 and 3.0 Hz, CH=CH); 13C-NMR (CDCl3, 100 MHz):
d (ppm) = 14.1 (q), 22.7 (t), 26.2 (t), 29.2 (t), 29.3 (t), 29.5 (t),
29.6 (t), 29.6 (t), 29.7 (t), 38.8 (d), 42.2 (d), 44.0 (d), 49.4 (t), 71.1
(t), 132.5 (d) and 137.0 (d); HR-MS calcd for C18H32O: m/z =
∑
273.1702 (M+ ).
1,3-Di(1-mesityl)-4-{[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)-
oxy]methyl}-4,5-dihydro-1H-imidazol-3-ium carboxylate (M3)
∑
264.2451, found m/z = 264.2453 (M+ ). Elemental analysis (%)
calcd for C18H32O: C, 81.75; H, 12.2, found: C, 81.6; H, 12.1.
1,3-Di(1-mesityl)-4-{[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)oxy]-
methyl}-4,5-dihydro-1H-imidazol-2-ium
tetrafluoroborate
Toluene-4-sulfonic acid 2-[2-(2-methoxy-ethoxy) ethoxy]-ethyl
ester
(500 mg, 0.91 mmol) was suspended in 20 mL of THF. Potassium
hydrate (55 mg, 1.37 mmol) was suspended in THF (5.0 mL) and
added to this suspension. The reaction mixture was stirred for
16 h and then filtered through Celite to remove residual salts. The
filtrate was transferred to a 50 mL Schlenk flask and removed
from the glove box. Carbon dioxide was bubbled through the
Triethyleneglycol monomethyl ether (5 mL, 0.032 mol),
p-toluenesulfonyl chloride (TosCl, 6.633 g, 0.035 mol, 1.1 eq.)
and pyridine (5.12 mL, 0.063 mol, 2 eq.) were dissolved in 31 mL
of CH2Cl2 and stirred at room temperature for 12 h. The solution
was filtered, concentrated in vacuo and dissolved in methyl-tert-
butylether. The precipitate was removed by filtration and the
filtrate was washed with 1 M HCl (2 ¥ 10 mL), NaHCO3 and
◦
solution at 0 C for 30 min, during this time a white precipitate
formed. The solvent was removed in vacuo, and the residue was
washed with diethyl ether and dried. Yield 345 mg (75.0%).
-1
¯
concentrated in vacuo to afford the tosylate (8.313 g, 83%) as
FT-IR (ATR mode, cm ): n = 2970 (w), 1737 (s), 1674 (s),
-1
¯
a colorless oil. FT-IR (ATR mode, cm ): n = 3034 (w), 2920
1606 (w), 1557 (s), 1473 (m), 1286 (s), 1157 (s), 1024 (m), 848
(m), 769 (m) and 718 (m); H-NMR (CDCl3, 600.25 MHz): d
1
(m), 2876 (m), 1598 (m), 1451 (m), 1354 (s), 1189 (s), 1176 (vs),
1096 (s br), 920 (s br), 817 (s), 775 (s), 663 (s); 1H-NMR (CDCl3,
400 MHz): d (ppm) = 2.45 (s, 3H, Ar-CH3), 3.37 (s, 3H, OCH3),
3.52 (m, 2H, OCH2CH2O), 3.59–3.62 (m, 6H, 3 ¥ OCH2CH2O),
3.69 (m, 2H, CH2CH2OSO2), 4.16 (m, 2H, CH2CH2OSO2), 7.34
(dd, 2H, J = 8.5 and 0.6 Hz, 2 ¥ Ar) and 7.80 (m, 2H, 2 ¥ Ar);
13C-NMR (CDCl3, 100 MHz): d (ppm) = d 21.7 (q), 53.5 (q), 68.7
(t), 69.3 (t), 70.6 (t), 70.6 (t), 70.8 (t), 72.0 (t), 126.3 (d), 129.9
(d), 133.1 (s) and 144.9 (s); HR-MS calcd for C14H22O6S: m/z =
(ppm) = 1.19–1.49 (3H, m, NBE), 1.89 (1H, m, NBE), 2.26 and
2.46 (18H, m, Mes), 2.72–3.25 (3H, m, NBE), 3.65–4.77 (5H, m,
NHC), 5.74–5.88 and 6.03–6.24 (2H, all m, NBE), 6.92 (4H, m,
Mes); 13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 17.8 and 20.7
(Mes), 29.6, 42.6 and 46.4 (all NBE), 49.9, 55.3, 60.9, 61.9 and
64.0 (all NHC), 130.1, 131.9, 133.6, 136.2, 138.3, 140.3 and 141.1
(all NBE + Mes), 154.3 (–N+ C–), 166.5 (CO2 ), 174.4, 175.8
-
=
=
(C O); FAB-MS calcd for C31H36N2O4: m/z = 500.2675, found
∑
319.1199, found m/z = 319.1215 (M+ ).
m/z = 501.3 (M + H)+.
5-{2-[2-(2-Methoxy-ethoxy)-ethoxy]-ethoxymethyl}-7-
Homopolymerization of M1
oxabicyclo[2.2.1]hept-2-ene (M2)
M1 (100 mg, 0.37 mmol) and RuCl2(Py)2(IMesH2)(CHPh)
(6.8 mg, 9.4 ¥ 10-3 mmol) were separately dissolved in chloroform
(each 2 mL). The monomer solution was added to the catalyst
solution and the resulting mixture was stirred vigorously for 14 h.
The polymerization was terminated by the addition of 1 mL ethyl
vinyl ether. The polymer was then precipitated by addition of
methanol, filtered off and dried. Yield: 85 mg (85%). Poly(M1):
7-Oxabicyclo[2.2.1]hept-5-en-2-ylmethanol (757 mg, 6.001 mmol)
was added dropwise to a suspension of NaH (288 mg,
12.002 mmol, 2 eq.) in 40 mL of dry DMF, under an inert
atmosphere. The mixture was stirred at room temperature for
10 min and at 60 ◦C for 1 h. Toluene-4-sulfonic acid 2-[2-
(2-methoxy-ethoxy) ethoxy]-ethyl ester (1.911 g, 6.001 mmol)
dissolved in 10 mL of DMF was added at room temperature.
The mixture was stirred at room temperature for 10 min and
at 60 ◦C for 12 h. Then H2O was added and the layers were
separated. The aqueous layer was extracted with ethyl acetate and
the combined organic layers were washed with NaHCO3 and brine,
dried over MgSO4 and concentrated in vacuo. The brown residue
was purified by column chromatography (SiO2, MTBE : acetone =
Mn(found) = 9600 g mol-1 (PDI = 1.16), Mn(calc) = 10 700 g mol-1;
-1
¯
FT-IR (ATR mode, cm ): n = 2921 (s), 2851 (s), 1455 (m), 1364
(w), 1110 (s), 968 (m), 734 (m); 1H-NMR (CDCl3, 600.25 MHz): d
(ppm) = 0.87 (br s, CH3), 1.26 and 1.53 (br s, CH2), 1.87, 2.21, 2.48,
2.63, 2.78 and 2.97 (br s, NBE), 3.18 and 3.35 (br s, –CH2–O–), 5.08
and 5.44 (br d, –CH CH–); 13C-NMR (CDCl3, 150.93 MHz): d
=
(ppm) = 14.2 (CH3), 22.8, 26.3, 29.4 and 32.0 (all CH2), 37.3, 39.3,
20 : 1) to afford M2 (646 mg, 41%) as a yellow oil. FT-IR (ATR
42.1 and 45.8 (all NBE), 71.3 and 72.8 (CH2–O–), 128.2, 130.0,
-1
=
¯
mode, cm ): n = 3076 (w), 2933 (m), 2869 (s), 1453 (m), 1351
133.8 and 134.6 (–CH CH–). cis : trans = 60 : 40.
9048 | Dalton Trans., 2009, 9043–9051
This journal is
The Royal Society of Chemistry 2009
©

Homopolymerization of M2
measurements in water and DMF, 6-p-toluidene-2-naphthylsu-
fonic acid (10-6 and 10-4 mol L-1) was used as fluorescence probe:
cmcwater = 1.5 ¥ 10-4 mol L-1; cmcDMF = 1.7 ¥ 10-4 mol L-1.
M2 (100 mg, 0.36 mmol) and RuCl2(Py)2(IMesH2)(CHPh)
(5.3 mg, 7.3 ¥ 10-3 mmol) were separately dissolved in chloroform
(each 2 mL). Polymerization and workup were conducted as
Synthesis of micellar catalyst
described for poly(M1). Yield: 75 mg (75%). Poly(M2): Mn(found)
=
12 600 g mol-1 (PDI = 1.19), Mn(calc) = 13 600 g mol-1; FT-IR (ATR
poly(M1-co-M3)-b-poly(M2) (200 mg) was suspended in 15 mL of
THF, then CuCl (10.0 mg, 0.10 mmol) was added. The mixture
was heated to 80 ◦C. After 3 h of stirring, the reaction mixture was
cooled to room temperature. The solution was filtered through a
glass fiber filter paper and dried. Yield: 184 mg (92%). The Cu
content was determined by ICP-OES after dissolving a 10.5 mg
sample in aqua regia and found to be 6.89 mg g-1 (0.108 mmol g-1).
-1
¯
mode, cm ): n = 2864 (s), 1456 (w), 1336 (w), 1293 (w), 1248 (w),
1
1196 (w), 1104 (s), 1029 (m); H-NMR (CDCl3, 600.25 MHz): d
(ppm) = 1.30–2.70 (br m, NBE), 3.33 (br s, CH3–O–), 3.50 and
3.60 (br s, –CH2–O–), 3.01, 4.35 and 4.69 (all br s, –CH–O–), 5.30–
5.80 (br d, –CH CH–); 13C-NMR (CDCl3, 62.90 MHz) 36.4, 43.3
=
and 45.6 (NBE), 59.0 (CH3–O–), 70.4 and 71.8 (CH2–O–), 81.9
=
(NBE), 129.2 and 132.8 (–CH CH–). cis : trans = 50 : 50.
ICO-OES measurements
Homopolymerization of M3
Cu was quantified using the emission wavelength at l =
324.754 nm. The background was measured at 324.670 nm and
324.809 nm, respectively. For calibration, Cu standards (dilute
HNO3) containing 0.1/1.0/10.0 mg L-1 of Cu were used.
M3 (100 mg, 0.2 mmol) and RuCl2(Py)2(IMesH2)(CHPh) (1.5 mg,
2 ¥ 10-3 mmol) were separately dissolved in chloroform (each
2 mL). Polymerization and workup were conducted as described
for poly(M1). Yield: 85 mg (85%). Poly(M3): Mn(found) = 80 400 g
mol-1 (PDI = 1.01), Mn(calc) = 50 000 g mol-1; FT-IR (ATR
CuCl(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)
-1
¯
mode, cm ): n = 2920 (w), 2860 (w), 1729 (m), 1655 (s), 1477
1,3-Dimesityl-3,4,5,6-tetrahydropyrimidin-1-ium-2-carboxylate49
(300 mg, 0.83 mmol) was suspended in 15 mL of toluene. Copper(I)
chloride (82.0 ◦mg, 0.82 mmol) was added, then the mixture was
heated to 100 C. After 1 h of stirring, the reaction mixture was
cooled to room temperature. The solvent was removed in vacuo,
and the residue was dissolved in dichloromethane. The solution
was filtered through glass fibre paper. Evaporation of the solvent
resulted in a white solid (327 mg, 95%). FTIR (ATR mode, cm-1):
(m), 1448 (w), 1377 (w), 1241 (m), 1157 (s), 1024 (w), 851 (m);
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 0.82–2.00 (br m,
NBE), 2.22 and 2.42 (br s, Mes), 2.60–3.38 (br, NBE), 3.50–4.60
(br m, NHC), 5.16, 5.48 and 5.58 (all br, NBE), 6.82 (br s, Mes);
13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 18.3 and 20.7 (Mes),
36.5, 40.8 and 48.2 (all NBE), 55.5, 57.5, 62.5 and 64.4 (all NHC),
=
129.9, 134.9 and 141.0 (–CH CH– and NBE), 164.6 (CO2), 174.0
=
and 175.1 (C O).
¯
n = 2907 (br), 1608 (s), 1509 (s), 1445 (s), 1340 (s), 1208 (s), 861
(s), 851 (s); 1H NMR (CDCl3, 250.13 MHz): d (ppm) 6.92 (s, 4H),
3.33 (t, 4H, J = 5.75 Hz), 2.27 (m, 20H of CH3 and CH2); 13C
NMR (CDCl3, 62.90 MHz): d (ppm) = 200.8 (CN), 142.0, 138.2,
134.5, 129.9, 44.24, 21.1, 20.9, 18.1. Crystals suitable for X-ray
analysis were obtained from CH2Cl2–diethyl ether.
Synthesis of poly(M1-co-M3)-b-poly(M2)
M1 (45.0 mg, 0.172 mmol) and M3 (17.2 mg, 0.034 mmol)
were dissolved in chloroform (2 mL) and added to a solution
of RuCl2(Py)2(IMesH2)(CHPh) (5 mg, 6.8 ¥ 10-3 mmol) in
chloroform (1 mL). The reaction mixture was stirred for 3 h
and a small amount of the reaction mixture was removed for
GPC measurements. M2 (150.0 mg, 0.550 mmol), dissolved in
chloroform (2 mL), was added to the reaction mixture. The
reaction mixture was stirred for another 14 h. The polymerization
was stopped with ethyl vinyl ether (3–4 drops) and stirred for
another 15 min. The polymer was precipitated by the addition
Typical click-reaction under micellar conditions
The micellar catalyst (0.2 mol% of Cu with respect to azide),
phenylacetylene (104.0 mg, 1.02 mmol) and benzyl azide
(136.6 mg, 1.03 mmol) were dissolved in a mixture of THF : water
(1 : 10). The mixture was stirred at room temperature for 16 h and
then filtered. All solvent was removed in vacuo, the crude product
was dissolved in dichloromethane and passed through a short pad
of silica (silica G60). The solvent was evaporated under vacuo and
white solid was recrystallized from dichloromethane and pentane.
Yield: 127.5 mg (53%). 46 ppm of Cu were found in the product.
of pentane, filtered off and dried. Yield: 155 mg (73%). FT-IR
-1
¯
(ATR mode, cm ): n = 2918 (m), 2858 (s), 1727 (w), 1627 (w),
1454 (w), 1355 (w), 1289 (w), 1248 (w), 1195 (w), 1100 (s), 1026
1
(m), 853 (w); H-NMR (CDCl3, 600.25 MHz): d (ppm) = 0.81
(br s, CH3), 1.20 (br s, CH2), 1.47, 1.77, 1.93, 2.16, 2.34 and 2.56
(all br s, NBE + CH2), 3.31 (br s, CH3–O–), 3.49 and 3.59 (br s,
Recyclability studies with poly(M1-co-M3)-b-poly(M2)–Cu in
click reactions
–CH2–O–), 3.96, 4.30 and 4.63 (all br s, –CH–O–), 5.00–5.75 (br
13
=
m, –CH CH–), 6.85 (br s, Mes); C-NMR (CDCl3, 150.93 MHz):
The micellar catalyst poly(M1-co-M3)-b-poly(M2)–Cu (1 mol%
of Cu with respect to the azide), phenylacetylene (51.2 mg,
0.50 mmol), 3-methylbenzylazide (74.0 mg, 0.50 mmol), and tert-
butylbenzene (40.0 mg, 0.30 mmol) were dissolved in a mixture
of THF : water (1 : 10). The reaction mixture was stirred at room
temperature for 8 h. Product conversion was monitored by
GC-MS. For additional cycles, the product was extracted by
using diethyl ether (4 ¥ 10 mL). Fresh phenylacetylene (51.2 mg,
d (ppm) = 14.1 (CH3), 52.9, 53.8 and 55.1 (NCH3), 59.4, 61.8 and
+
=
64.6 (all CH2), 77.2 (NBE), 132.7(–CH CH–), 157.8 (–N –C–),
=
162.3 (CO2), 173.7 and 175.3 (C O).
Cmc-determination
The critical micellar concentration (cmc) of poly(M1-co-M3)-
b-poly(M2) was determined by fluorescence spectroscopy. For
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 9043–9051 | 9049
©

0.50 mmol), and 3-methylbenzylazide (74.0 mg, 0.50 mmol),
and tert-butylbenzene (40.0 mg, 0.30 mmol) were added to the
aqueous, catalyst-containing phase and the reaction was run under
the same conditions as before. Four consecutive cycles were carried
out. The yield in these four consecutive cycles as determined by
GC-MS (vide supra) was 100, 100, 100 and 95%, respectively.
1-(3-Methylbenzyl)-4-phenyl-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 2.35 (3H, s, CH3),
5.53 (2H, s, CH2), 7.09–7.21 (3H, m, Ar), 7.27–7.34 (2H, m, Ar),
7.40 (2H, t, J = 6.00 Hz, Ar), 7.66 (1H, s, triazole), 7.80 (2H,
m, Ar); 13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 21.4, 54.3,
119.6, 125.2, 125.8, 128.2, 128.9 (d), 129.1, 129.6, 130.7, 134.7,
139.1, 148.3. ESI-MS calcd For C16H15N3: m/z = 249.31, found
m/z = 250.1 (M + H)+.
1-Benzyl-4-phenyl-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 5.58 (2H, s, CH2),
7.28–7.41 (8H, m, Ar), 7.66 (1H, s, triazole), 7.80 (2H, d, J =
6.00, Ar); 13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 54.3, 119.6,
125.8, 128.1, 128.2, 128.9, 129.2, 130.6, 134.8, 148.3; ESI-MS calcd
for C15H13N3: m/z = 235.11; found m/z = 258.0 (M + Na)+.
1-(4-tert-Butylbenzyl)-4-phenyl-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 1.32 (9H, S, CH3),
5.54 (2H, s, CH2), 7.24–7.28 (2H, m, Ar), 7.31 (1H, m, Ar), 7.40
(4H, m, Ar), 7.66 (1H, s, triazole), 7.81 (2H, m, Ar); 13C-NMR
(CDCl3, 150.93 MHz): d (ppm) = 31.3, 34.7, 54.0, 119.5, 125.8,
126.2, 128.0, 128.2, 128.9, 130.7, 131.7, 148.2, 152.0. ESI-MS calcd
for C19H21N3: m/z = 291.39, found m/z = 292.1 (M + H)+.
1-Benzyl-4-(4-methoxyphenyl)-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 3.83 (3H, s, CH3),
5.56 (2H, s, CH2), 6.94 (2H, d, J = 12.00 Hz, Ar), 7.28–7.42 (5H,
m, Ar), 7.58 (1H, s, triazole), 7.72 (2H, d, J = 6.00 Hz, Ar);
13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 54.3, 54.4, 114.3,
118.8, 123.4, 127.1, 128.1, 128.8, 129.2, 134.9, 148.2, 159.7M;
ESI-MS calcd for C16H15N3O: m/z = 265.12; found m/z = 288.1
(M + Na)+.
Hydrosilylation of carbonyl compounds in DMF
The micellar catalyst (0.05 mol% Cu with respect to the carbonyl
compound) was dissolved in 1 mL of DMF, potassium tert-
butoxide (0.15 mol eq.) and the carbonyl compound (1.42 mmol)
were added and the solution was stirred for 5 min. Then, 4 mol
eq. of triethylsilane (0.20–0.40 mmol) were added to the reaction
mixture. The solution was heated to 60 ◦C. Product conversion was
monitored by GC-MS at defined time intervals. Compounds were
identified by GC-MS. Quantification was accomplished using an
internal standard (tert-butylbenzene).
1-Benzyl-4-(4-fluorophenyl)-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 5.57 (2H, s, CH2), 7.09
(2H, m, Ar), 7.29–7.42 (5H, m, Ar), 7.62 (1H, s, triazole), 7.76 (2H,
m, Ar); 13C-NMR (CDCl3, 150.93 MHz): d (ppm) = 54.3, 115.8,
115.9, 119.3, 126.8, 127.5 (d), 128.2, 128.9, 129.3, 134.7, 147.5,
161.9, 163.6; ESI-MS calcd for C15H12FN3: m/z = 253.10; found
m/z = 254.1 (M + H)+.
X-Ray measurement and structure determination of 1†
Data collection was performed on a Nonius Kappa CCD
equipped with graphite-monochromatized Mo Ka radiation (l =
˚
0.71073 A) and a nominal crystal to area detector distance of
4-Phenyl-1-(phenylthiomethyl)-1H-1,2,3-triazole
36 mm. Intensities were integrated using DENZO and scaled
with SCALEPACK.54 Several scans in f and w direction were
made to increase the number of redundant reflections, which
were averaged in the refinement cycles. This procedure replaces
in a good approximation an empirical absorption correction. The
structures were solved with direct methods SHELXS86 and refined
against F2 SHELX97.55 All non-hydrogen atoms were refined with
anisotropic displacement parameters and all hydrogen atoms were
calculated and refined, using a riding model.
1H-NMR (CDCl3, 250.13 MHz): d (ppm) = 5.56 (2H, s, CH2),
7.33 (8H, m, Ar), 7.78 (3H, m); 13C-NMR (CDCl3, 150.93 MHz):
d (ppm) = 54.0, 119.1, 125.8, 128.4, 128.8, 128.9, 129.6, 130.4,
131.9, 132.3, 148.3; ESI-MS calcd for C15H13N3S: m/z = 267.08;
found m/z = 290.0 (M + Na)+.
4-(4-Methoxyphenyl)-1-(phenylthiomethyl)-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 3.83 (3H, s, CH3),
5.64 (2H, s, CH2), 6.95 (2H, d, J = 12.00 Hz, Ar), 7.28–7.40 (5H,
m, Ar), 7.69 (3H, m); 13C-NMR (CDCl3, 150.93 MHz): d (ppm) =
53.9, 55.4, 114.3, 118.2, 123.1, 127.1, 128.8, 129.6, 132.0, 132.3,
178.2, 159.8; ESI-MS calcd for C16H15N3OS: m/z = 297.09; found
m/z = 320.1 (M + Na)+.
Acknowledgements
We are grateful to Dr Wolfgang Geyer (UFZ, Leipzig) for
his kind help with fluorescence measurements. This work was
supported by the Federal Government of Germany and the
Freistaat Sachsen, the Cluster of Excellence “Unifying concepts
in Catalysis” coordinated by the TU Berlin and funded by the
Deutsche Forschungsgemeinschaft.
4-(4-Fluorophenyl)-1-(phenylthiomethyl)-1H-1,2,3-triazole
1H-NMR (CDCl3, 600.25 MHz): d (ppm) = 5.65 (2H, s, CH2),
7.10 (2H, m, Ar), 7.28–7.39 (5H, m, Ar), 7.74 (3H, m); 13C-NMR
(CDCl3, 150.93 MHz): d (ppm) = 54.0, 115.8, 116.0, 118.8, 126.6
(d), 127.5 (d), 128.8, 129.6, 131.9, 132.2, 147.5, 161.9, 163.6; ESI-
MS calcd for C15H12FN3S: m/z = 285.07, found m/z = 308.0
(M + Na)+.
References
1 P. Zheng, X. Jiang, X. Zhang, W. Zhang and L. Shi, Langmuir, 2006,
22, 9393.
2 B. Jeong, Y. H. Bae, D. S. Lee and S. W. Kim, Nature, 1997, 388, 860.
3 T. P. Lodge, Macromol. Chem. Phys., 2003, 204, 265.
9050 | Dalton Trans., 2009, 9043–9051
This journal is
The Royal Society of Chemistry 2009
©

4 K. Stubenrauch, C. Moitzi, G. Fritz, O. Glatter, G. Trimmel and F.
Stelzer, Macromolecules, 2006, 39, 5865.
5 I. W. Hamley and V. Castelletto, Prog. Polym. Sci., 2004, 29, 909.
6 B. Cornils and W. A. Herrmann, Aqueous Phase Organometallic
Catalysis-Concepts and Application, Wiley-VCH, Weinheim, Germany,
1998.
32 M. R. Buchmeiser, J. Mol. Catal. A: Chem., 2002, 190, 145.
33 M. Mayr, M. R. Buchmeiser and K. Wurst, Adv. Synth. Catal., 2002,
344, 712.
34 J. H. Oskam, H. H. Fox, K. B. Yap, D. H. McConville, R. O’Dell,
B. J. Lichtenstein and R. R. Schrock, J. Organomet. Chem., 1993, 459,
185.
7 T. Kotre, O. Nuyken and R. Weberskirch, Macromol. Rapid. Commun.,
2002, 23, 871.
35 M. R. Buchmeiser, M. Mupa, G. Seeber and G. K. Bonn, Chem. Mater.,
1999, 11, 1533.
8 J. O. Krause, M. T. Zarka, U. Anders, R. Weberskirch, O. Nuyken and
M. R. Buchmeiser, Angew. Chem., 2003, 115, 6147; J. O. Krause, M. T.
Zarka, U. Anders, R. Weberskirch, O. Nuyken and M. R. Buchmeiser,
Angew. Chem., Int. Ed., 2003, 42, 5965.
9 M. T. Zarka, M. Bortenschlager, K. Wurst, O. Nuyken and R.
Weberskirch, Organometallics, 2004, 23, 4817.
36 M. Mayr, D. Wang, R. Kro¨ll, N. Schuler, S. Pru¨hs, A. Fu¨rstner and
M. R. Buchmeiser, Adv. Synth. Catal., 2005, 347, 484.
37 J. P. Gallivan, J. P. Jordan and R. H. Grubbs, Tetrahedron Lett., 2005,
46, 2577.
38 S. H. Hong and R. H. Grubbs, J. Am. Chem. Soc., 2006, 128,
3508.
10 Y. Uozumi, H. Tanaka and K. Shibatomi, Org. Lett., 2004, 6, 281.
11 D. E. Bergbreiter, Chem. Rev., 2002, 102, 3345.
12 M. T. Zarka, O. Nuyken and R. Weberskirch, Macromol. Rapid
Commun., 2004, 25, 858.
13 S. R. Gilbertson, X. Wang, G. S. Hoge, C. A. Klug and J. Schaefer,
Organometallics, 1996, 15, 4678.
14 S. R. Gilbertson and X. Wang, Tetrahedron Lett., 1996, 37, 6475.
15 Y. Uozumi, H. Danjo and T. Hayashi, Tetrahedron Lett., 1997, 38, 3557.
16 H. Danjo, D. Tanaka, T. Hayashi and Y. Uozumi, Tetrahedron, 1999,
55, 14341.
39 W. J. Sommer and M. Weck, Adv. Synth. Catal., 2006, 348, 2101.
40 W. A. Herrmann, M. Elison, J. Fischer, C. Kocher and C. R. J. Artus,
Angew. Chem., 1995, 107, 2602; W. A. Herrmann, M. Elison, J. Fischer,
C. Kocher and C. R. J. Artus, Angew. Chem., Int. Ed. Engl., 1995, 34,
2371.
41 W. A. Herrmann, M. Elison, J. Fischer, C. Kocher and C. R. J. Artus,
Chem.–Eur. J., 1996, 2, 772.
42 T. M. Trnka and R. H. Grubbs, Acc. Chem. Res., 2001, 34, 18.
43 N. J. Whitcombe, K. K. Hii and S. E. Gibson, Tetrahedron, 2001, 57,
7449.
17 Y. Uozumi, H. Danjo and T. Hayashi, J. Org. Chem., 1999, 64, 3384.
18 Y. Uozumi and T. Watanabe, J. Org. Chem., 1999, 64, 6921.
19 Y. Uozumi and Y. Nakai, Org. Lett., 2002, 4, 2997.
20 Y. Uozumi and T. Kimura, Synlett, 2002, 2045.
44 W. A. Herrmann, K. Ofele, D. Von Preysing and S. K. Schneider,
J. Organomet. Chem., 2003, 687, 229.
45 B. Bantu, D. Wang, K. Wurst and M. R. Buchmeiser, Tetrahedron,
2005, 61, 12145.
46 S. D´ıez-Gonza´lez, N. M. Scott and S. P. Nolan, Organometallics, 2006,
25, 2355.
47 L. Delaude, Eur. J. Inorg. Chem., 2009, 1681.
48 M. J. Beier, W. Knolle, A. Prager-Duschke and M. R. Buchmeiser,
Macromol. Rapid Commun., 2008, 29, 904.
21 H. Hocke and Y. Uozumi, Synlett, 2002, 2049.
22 Y. Uozumi and Y. Kobayashi, Heterocycles, 2003, 59, 71.
23 W. A. Herrmann and C. W. Kohlpaintner, Angew. Chem., Int. Ed. Engl.,
1993, 32, 1524.
24 S. Kobayashi and S. Nagayama, J. Am. Chem. Soc., 1996, 118, 8977.
25 B. A. Kulkarni and A. Ganesan, Chem. Commun., 1998, 785.
26 S. C. Schu¨rer, S. Gessler, N. Buschmann and S. Blechert, Angew. Chem.,
2000, 112, 4062; S. C. Schu¨rer, S. Gessler, N. Buschmann and S.
Blechert, Angew. Chem., Int. Ed., 2000, 39, 3898.
49 B. Bantu, G. M. Pawar, U. Decker, K. Wurst, A. M. Schmidt and M. R.
Buchmeiser, Chem.–Eur. J., 2009, 15, 3103.
50 H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem., 2001, 113,
2056.
27 S. Randl, N. Buschmann, S. J. Connon and S. Blechert, Synlett, 2001,
1547.
51 C. W. Tornøe, C. Christensen and M. Meldal, J. Org. Chem., 2002, 67,
3057.
28 F. Sinner and M. R. Buchmeiser, Angew. Chem., 2000, 112, 1491; F.
Sinner and M. R. Buchmeiser, Angew. Chem., Int. Ed., 2000, 39, 1433.
29 F. Sinner and M. R. Buchmeiser, Macromolecules, 2000, 33, 5777.
30 M. Mayr, B. Mayr and M. R. Buchmeiser, Angew. Chem., 2001, 113,
3957; M. Mayr, B. Mayr and M. R. Buchmeiser, Angew. Chem., Int.
Ed., 2001, 40, 3839.
52 H. Kaur, F. Zinn Kauer, E. D. Stevens and S. P. Nolan, Organometallics,
2004, 23, 1157.
53 T.-L. Choi and R. H. Grubbs, Angew. Chem., 2003, 115, 1785; T.-L.
Choi and R. H. Grubbs, Angew. Chem., Int. Ed. Engl., 2003, 42, 1743.
54 Z. Otwinowski and W. Minor, Methods in Enzymology, Academic Press,
New York, 1997, 276, 307.
31 S. Lubbad, B. Mayr, M. Mayr and M. R. Buchmeiser, Macromol.
Symp., 2004, 210, 1.
55 G. M. Sheldrick, Program package SHELXTL V.5.1, Bruker Analytical
X-Ray Instruments Inc, Madison, USA, 1997.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 9043–9051 | 9051
©