Dalton Transactions
ARTICLE
5DT01825K
DOI: 10.1039Jo/Curnal Name
delivered (over 28 s for each injection). The corresponding heat flow (1.5 mL) and heptane (1.5 mL) and the resulting solution was poured
was recorded as a function of time. The time interval between two onto the aqueous phase. The mixture was stirred at 800 rpm and
consecutive injections was 250 s and stirring speed was 304 rpm for maintained at 25 °C or 45 °C for 18 h under 1 bar H . Once the
2
all experiments. In addition, the heat consecutive to dilution was reaction was complete, the organic phase was recovered by simple
eliminated by performing blank titrations. The areas under the peak decantation and the aqueous phase was washed with toluene. The
following each injection (obtained by integration of the raw signal) organic phases were combined and evaporated. The products were
were then expressed as the heat effect per mole of added 1. Binding purified by column chromatography over silica gel (conditioned with
constants and inclusion enthalpies were finally determined by heptane) using a heptane/acetone (9/1) mixture as eluant. All
nonlinear regression analysis of the binding isotherms using a built- products were analyzed by GC-MS by comparison with references.
in binding model (one set of sites) within MicroCal Origin 7.0
software package (MicroCal, Northampton, MA).
Recycling procedure
Synthetic procedures
After decantation, the recovered catalytic aqueous phase was filtered
under nitrogen on Celite which was washed with 0.5 mL degassed
Preparation
of
randomly
methylated
1-(6A-Deoxy-β-D- water. No Pt particle could be detected on Celite. The filtrate was
cyclodextrin)-4-[(dimethylamino)methyl]-1,2,3-triazole
(1): lyophilized and dissolved in 1 mL degassed water. Fresh substrates
Randomly methylated mono-6-azido-6 -deoxy-β-D-cyclodextrin were then added and the reaction was restarted.
812 mg, 0.6 mmol) and hydrated copper sulfate (175 mg, 0.7 mmol)
were added to a solution of N,N-dimethylpropargylamine (58 mg, Acknowledgements
.7 mmol) in DMF (30 mL). After the subsequent dropwise addition Roquette Frères (Lestrem, France) is gratefully acknowledged
A
(
0
of a freshly prepared solution of sodium ascorbate (277 mg, 1.4 for generous gifts of cyclodextrins. We thank Dr. Nicolas Kania
mmol) dissolved in water (3 mL) the solution was stirred for 18 h at and D. Prevost for technical assistance.
room temperature. After evaporation of the solvent the crude product
was dissolved in an ammoniac solution (10%) and stirred overnight
before being purified by column chromatography on silica gel with
Notes and references
a
Université d'Artois, Unité de Catalyse et de Chimie du Solide - UCCS,
water as eluent to give the product as a white powder. Yield: 589
1
CNRS UMR 8181, Faculté des Sciences Jean Perrin, SP18, 62307 Lens
Cedex, France. E-mail: frederic.hapiot@univ-artois.fr.
mg, 0.41 mmol, 83%. H NMR (300 MHz, D O): δ = 8.27 (s, 1 H),
2
5
3
.19 (m, 4.9 H), 4.98 (m, 50H), 4.44 (m, 2.1 H), 4.13 (m, 3.1 H),
.98–3.88 (m, 13.1 H), 3.68–3.53 (m, 43.9 H), 3.47–3.29 (m, 17.9
b
Université du Littoral, UCEIV – ULCO, 145 Avenue Maurice
1
3
H), 2.82 (s, 6 H) ppm. C NMR (75.5 MHz, D O): δ = 137.4, 135.2, Schumann, MREI 1, 59140 Dunkerque, France.
2
1
7
12.8, 101.4–99.8, 99.0–97.4, 82.7–81.6, 78.5, 73.4, 73.3, 73.1,
2.6, 72.3, 72.2, 70.9, 70.3, 64.4–59.4, 42.4, 30.2, 20.2, 19.7 ppm.
Electronic Supplementary Information (ESI) available: cyclodextrin
structure, NMR data. See DOI: 10.1039/b000000x/
MS: m/z (%) = 1433.51 (11.6) (calcd. 1433.57 for [C H N O +
Na] ), 1447.53 (69.9) (calcd.1447.58 for [C H N O + Na] ),
1
5
9
102
4
34
+
+
6
0
104
4
34
+
1
2
D. Morales-Morales, C. M. Jensen, (Eds.) The Chemistry of Pincer
Compounds, Elsevier, Amsterdam, 2007.
461.55 (16.1) (calcd. 1461.59 for [C H N O + Na] ), 1477.05
61 106 4 34
+
(2.3) (calcd. 1475.6 for [C H N O + Na] ).
62 108 4 34
The Pincer Ligand: Its Chemistry and Applications (Catalytic
Science) (Eds: P. A. Chase, G. Van Koten), Imperial College Press,
London, 2012.
-
2
Preparation of Pt-complexes 4: RAME-β-CD (13.1 mg, 10 mmol),
ligand 3 (5.1 mg, 10 mmol) and K PtCl (4.1 mg, 10 mmol) were
successively dissolved in 1 mL degassed D O. The resulting solution
was immediately analyzed by NMR. The mixture was then heated at
-
2
-2
2
4
2
3
4
5
G. van Koten and R. J. M. Klein Gebbink, Pincers and other
hemilabile ligands, Dalton Trans., 2011, 35, 8713.
7
0 °C for 15 min and cooled down to 25 °C, temperature at which a
S. Schneider, J. Meiners and B. Askevold, Eur. J. Inorg. Chem.
012, 412.
E. Y. Bezsoudnova and A. D. Ryabov, J. Organomet. Chem., 2001,
22, 38.
,
second set of NMR spectra was collected.
2
-
2
Preparation of Pt-complex 7: Compound 1 (14.2 mg, 10 mmol),
ligand 3 (5.1 mg, 10 mmol) and K PtCl (4.1 mg, 10 mmol) were
dissolved in 1 mL degassed D O. The resulting solution was heated
a 70 °C for 15 min and a first set of NMR spectra was collected.
After addition of excess K CO (6.9 mg, 5.10 mmol) at 70 °C, the
solution was stirred for another 15 min. The solution was cooled
down and a second set of NMR spectra was collected.
6
-
2
-2
2
4
6
7
8
L. Botella and C. Nájera, J. Organomet. Chem., 2002, 663, 46.
L. Botella and C. Nájera, Angew. Chem. Int. Ed., 2002, 41, 179.
H.-J. van Manen, R. H. Fokkens, F. C. J. M. van Veggel and D. N.
Reinhoudt, Eur. J. Org. Chem., 2002, 3189.
2
-
2
2
3
9
1
R. Huang and K. H. Shaughnessy, Organometallics, 2006, 25, 4105.
0 C. Crisóstomo-Lucas, R. A. Toscano and D. Morales-Morales,
Tetrahedron Lett., 2013, 54, 3116.
Preparation of Pt-complexes 10: Complex 10 was synthesized
following the experimental procedure described for 7 from 2 (3.0
mg, 10 mmol) instead of 1.
-
2
11 V. F. Slagt, P. W. N. M. van Leeuwen and J. N. H. Reek, Chem.
Commun., 2003, 2474.
1
1
2 B. Breit and W. Seiche, J. Am. Chem. Soc., 2003, 125, 6608.
3 J. M. Takacs, D. S. Reddy, S. A. Moteki, D. Wu and H. Palencia,
Am Chem Soc., 2004, 126, 4494.
Catalytic experiments
J
-
3
In 3 mL degassed water were consecutively introduced 1 (7.10
-
3
-3
mmol, 10 mg), 3 (7.10 mmol, 3.7 mg) and K PtCl (7.10 mmol, 3
2
4
1
1
4 M. Raynal, P. Ballester, A. Vidal-Ferrana and P. W. N. M. van
Leeuwen, Chem. Soc. Rev., 2014, 43, 1660.
mg). The mixture was heated at 70 °C for 15 min and then cooled to
room temperature. The nitrobenzene derivative (1 mmol) and
hexane-2,5-dione (1 mmol, 114 mg) were dissolved in diethyl ether
5 C. Machut, J. Patrigeon, S. Tilloy, H. Bricout, F. Hapiot and E.
Monflier, Angew. Chem., Int. Ed., 2007, 46, 3040.
1
0 | J. Name., 2012, 00, 1-3
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