Towards Polymer Diagnostics
(s, 2 H, NCH2Ph), 3.84 (s, 4 H, pyCH2), 5.23 (d, Jcis = 11 Hz, 1
FULL PAPER
nochromated Mo-Kα radiation (λ = 0.71073 Å). Suitable crystals
3
3
H, cis-CH2CH), 5.75 (d, Jtrans = 18 Hz, 1 H, trans-CH2CH), 6.72 were covered with Paratone N oil, mounted on a glass fibre and
(dd, 1 H, CH2CH), 7.1–7.9 (m, 10 H, aromatic H), 8.56 ppm (m,
2 H, pyH6). 13C{1H} NMR (500 MHz, CDCl3): δ = 58.6, 60.4,
113.9, 123.2, 126.6, 129.4, 129.4, 136.9, 136.9, 137.0, 139.0, 149.4,
immediately transferred to the diffractometer. 8000 Reflections dis-
tributed over the whole limiting sphere were selected by the pro-
gram SELECT and used for unit cell parameter refinement with
160.2 ppm. IR (KBr): ν = 2922, 2821, 1629, 1590, 1569, 825, the program CELL.[13] Data were collected for Lorentz and polari-
˜
760 cm–1. FAB+ MS (NBA matrix): m/z (%) 316 (59) [(pyCH2)2- sation effects as well as for absorption (numerical). Structures were
NCH2PhCHCH2 + H]+, 223 (45) [pyCH2NCH2PhCHCH2]+, 198 solved by direct methods using SIR97[14] and were refined by full-
(26) [(pyCH2)2N]+, 117 (100) [CH2C6H4CHCH2]+, 93 (56) [pyCH2]+. matrix least-squares methods on F2 with SHELXL-97.[15]
General Procedure for the Preparation of Re(CO)3 Complexes: Un-
der an inert gas atmosphere, AgOTf (129 mg, 500 µmol) and
Re(CO)5Br (0.2 g, 0.5 mmol) in methanol were heated to reflux for
60 min. The AgBr precipitate was removed by filtration and
0.5 mmol of the ligand (1a or 1b) dissolved in 5 mL methanol was
added. The solution was refluxed for an additional hour. After
cooling to ambient temperature the solvent was removed in vacuo
and the residue dissolved in a minimum of dichloromethane. n-
Hexane was added to the solution and colourless crystals deposited
after a few days.
CCDC-617234 and -617235 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
B. S. thanks the Swiss National Science Foundation and the Uni-
versity of Zürich for financial support.
1
[(1a)Re(CO)3]OTf (2a): Yield: 0.28 g (76%). H NMR (500 MHz,
[1] H. Ringsdorf, J. Pharm. Sci. Polymer Symp. 1975, 51, 135–153.
[2] a) R. Duncan, S. Gac-Brenton, R. Keane, R. Musila, Y. N. Sat,
R. Satchi, F. Searle, J. Controlled Release 2001, 74, 135–146;
b) R. Duncan, Nat. Rev. Drug Discovery 2003, 2, 347–360.
[3] H. Maeda, J. Wu, T. Sawa, Y. Matsumura, K. Hori, J. Con-
trolled Release 2000, 65, 271–284.
CDCl3); δ = 4.69 (s, 2 H, PhCH2), 4.82 (m, 4 H, [AB]2, pyCH2),
7.1–7.9 (m, 11 H, aromatic H), 8.6 ppm (m, 2 H, pyH6). IR (KBr):
ν = 2028, 1922, 1612 cm–1. FAB+ MS (NBA matrix): m/z (%) 560
˜
(100) [(1a)Re(CO)3]+. C23H19F3N3O6ReS·CH2Cl2·C6H14 (879.80):
calcd. C 39.0, H 2.7, N 5.9; found C 38.6, H 2.7, N 5.8.
[4] E. Oberdisse, E. Hackenthal, K. Kuschinsky, Pharmakologie
und Toxikologie, 3rd ed., Springer, Berlin, 2002.
1
[(1b)Re(CO)3]OTf (2b): Yield: 0.27 g (75%). H NMR (500 MHz,
CDCl3); δ = 4.67 (s, 2 H, PhCH2), 4.82 (m, 4 H, [AB]2, pyCH2),
[5] a) A. Mitra, A. Nan, H. Ghandehari, E. McNeill, J. Mulhol-
land, B. R. Line, Pharm. Res. 2004, 21, 1153–1159; b) R. Sat-
chi-Fainaro, M. Puder, J. W. Davis, H. T. Tran, D. A. Sampson,
A. K. Greene, G. Corfas, J. Kolkman, Nat. Med. (N.Y.) 2004,
255–261; c) Y. Huang, A. Nan, G. M. Rosen, C. S. Winalski,
E. Schneider, P. Tsai, H. Ghandehari, Macromol. Biosci. 2003,
3, 647–652.
[6] K. Schwochau, Technetium, Wiley-VCH, Weinheim, 2000.
[7] a) R. Alberto, K. Ortner, N. Wheatley, R. Schibli, A. P. Schu-
biger, J. Am. Chem. Soc. 2001, 123, 3135–3136; b) R. Schibli,
R. Schwarzbach, R. Alberto, K. Ortner, H. Schmalle, C.
Dumas, A. Egli, A. P. Schubiger, Bioconjugate Chem. 2002, 13,
750–756; c) S. R. Banerjee, M. K. Levadala, N. Lazarova, L.
Wei, J. F. Valliant, K. A. Stephenson, J. W. Babich, K. P.
Maresca, J. Zubieta, Inorg. Chem. 2002, 41, 64–6425; d) T.
Storr, Y. Sugai, Y. Mikata, M. J. Adam, S. Yano, C. Orvig,
Inorg. Chem. 2005, 44, 2698–2705; e) N. Lazavora, J. Babich,
J. Valliant, P. Schaffer, S. James, J. Zubieta, Inorg. Chem. 2005,
44, 6763–6770.
3
3
5.31 (d, Jcis = 11 Hz, 1 H, cis-CH2CH), 5.78 (d, Jtrans = 18 Hz, 1
H, trans-CH2CH), 6.69 (dd, 1 H, CH2CH), 7.1–7.9 (m, 10 H, aro-
matic H), 8.6 (m, 2 H, pyH6). IR (KBr): ν = 2028, 1920, 1560 cm–1.
˜
FAB+ MS (NBA matrix): m/z (%) 585 (100) [(1b)Re(CO)3]+.
C25H21F3N3O6ReS·CH2Cl2·C6H14 (905.84): calcd. C 40.9, H 2.9, N
5.7; found C 40.1, H 2.6, N 5.6.
General Procedure for the Preparation of HPMA-co-bis(2-pyr-
idylmethyl)-4-vinylbenzylamine Copolymers (3): HPMA and bis(2-
pyridylmethyl)-4-vinylbenzylamine were dissolved in 15 mL of ace-
tone in a Schlenk tube under an inert gas atmosphere. After ad-
dition of AIBN, the solution was heated to 50 °C and stirred for
24 h. The polymer was then precipitated by pouring the reaction
mixture into a mixture of acetone and diethyl ether (1:1), the pre-
cipitate was filtered off and dried in vacuo to give 3a (1.5 g, 67%).
1H NMR (200 MHz, [D4]methanol): δ = 1.0 [CH2 (polymer back-
bone), HPMA-H1], 2.0 (HPMA-H4), 3.6 (HPMA-H3), 3.8
(NCH2Ph), 3.9 (pyCH2), 4.0 (HPMA-H2), 7.1–7.9 (aromatic H),
[8] S. Dick, A. Weiss, Z. Naturforsch., Teil B 1997, 52, 188–192.
[9] D. R. van Staveren, E. Bothe, T. Weyhermüller, N. Metzler-
Nolte, Eur. J. Inorg. Chem. 2002, 1518–1529.
8.6 ppm (pyH6). IR (KBr): ν = 2980, 2800, 1597, 1572, 749 cm–1.
˜
General Procedure for the Preparation of Re(CO)3-Labelled
HPMA-co-bis(2-pyridylmethyl)-4-vinylbenzylamine Copolymers (4):
Under an inert gas atmosphere, (nBu4N)2[Re(CO)3Br3] (0.1 g,
0.13 mmol) and AgOTf (0.11 g, 0.39 mmol) were heated to reflux
in methanol for 60 min. Precipitated AgBr was removed by fil-
tration and 0.458 g of the copolymer 3a dissolved in 10 mL meth-
anol was added. The solution was refluxed for an additional hour
and then cooled to room temperature. The polymer was then pre-
cipitated in a mixture of acetone and diethyl ether (1:1), filtered off
and dried in vacuo (0.46 g, 93%). 1H NMR ([D4]methanol): δ =
1.0 [CH2 (polymer backbone), HPMA-H1], 2.0 (HPMA-H4), 3.6
(HPMA-H3), 3.9 (pyCH2), 4.0 (HPMA-H2), 7.1–7.9 (aromatic H),
[10] Freshly prepared 1b was used as 1b homo-polymerises. Al-
though 1b has not been described in the literature, the homo-
polymer of 1b is known as Dowex B by the Dow Chemical
company.
[11] H. J. Hoorn, P. de Joode, W. L. Driessen, J. Reedijk, Recl. Trav.
Chim. Pays-Bas 1996, 115, 191–197.
[12] D. Vitali, F. Calderazzo, Gazz. Chim. Ital. 1972, 102, 587–596;
E. O. Brimm, M. A. Lynch Jr., W. J. Sesny, J. Am. Chem. Soc.
1954, 76, 3831–3835.
[13] “CELL” 2.87, 5/1998 ed., STOE & Cie, GmbH, Darmstadt,
Germany, 1998.
[14] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[15] SHELXL-97, G. M. Sheldrick, University of Göttingen, Ger-
many, 1997.
8.5 ppm (pyH6). IR (KBr): ν = 2980, 2800, 2033 (νCO), 1933 (νCO),
˜
1612, 1598, 749 cm–1.
X-ray Crystallographic Study: Crystallographic data were collected
with a Stoe IPDS diffractometer at 183(2) K using a graphite-mo-
Received: September 5, 2006
Published Online: November 29, 2006
Eur. J. Inorg. Chem. 2007, 394–399
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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